KR20210057703A - Protective film forming film, protective film forming composite sheet, inspection method and identification method - Google Patents

Abstract

The present invention provides a protective film-forming film 13 having an image clarity of 110 or more, a protective film-forming composite sheet having the same, and an inspection method and an identification method. The film 13 for forming a protective film of the present invention is affixed on the back surface of a semiconductor wafer to be laser printed, and is used for manufacturing a semiconductor chip with a protective film formed thereon.

Description

Protective film forming film, protective film forming composite sheet, inspection method and identification method

The present invention relates to a protective film-forming film, a protective film-forming composite sheet, an inspection method, and an identification method.

This application claims priority based on Japanese Patent Application No. 2018-169591 for which it applied to Japan on September 11, 2018, and uses the content here.

In recent years, semiconductor devices to which a mounting method called a so-called face down method is applied are being manufactured. In the face-down method, a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to the substrate. For this reason, the rear surface of the semiconductor chip opposite to the circuit surface can be exposed.

On the back surface of the exposed semiconductor chip, a protective film containing an organic material is formed, and it can be included in a semiconductor device as a semiconductor chip with a protective film formed thereon. The protective film is used to prevent the occurrence of cracks in the semiconductor chip after the dicing process or packaging.

In order to form such a protective film, for example, a composite sheet for forming a protective film comprising a film for forming a protective film for forming a protective film on a support sheet is used. The protective film-forming film can form a protective film by curing. Further, the support sheet can be used to fix the semiconductor wafer when dividing a protective film-forming film or a semiconductor wafer having a protective film on the back surface into semiconductor chips. In addition, the supporting sheet can also be used as a dicing sheet, and the protective film-forming composite sheet can be used as an integrated protective film-forming film and a dicing sheet (see, for example, Patent Document 1).

The film for protective film formation described in Patent Document 1 has an infrared ray transmittance at a wavelength of 1600 nm of 72% or more and a visible ray transmittance at 550 nm of 20% or less. Thereby, printing processing by irradiation of laser light is possible, and inspection by infrared rays such as cracks existing in the work or the work obtained by processing the work is possible.

When manufacturing a semiconductor chip with a protective film formed using the composite sheet for forming a protective film provided with the film for forming a protective film described in Patent Document 1, for example, first, a composite sheet for forming a protective film is affixed to the back surface of the semiconductor wafer. Subsequently, after laser printing on the protective film forming film, the semiconductor wafer is divided into chips by dicing and picked up after curing by heat or energy rays as necessary in order to increase the protective performance of the protective film forming layer. Subsequently, the semiconductor chip on which the picked up protective film is formed is usually subjected to a heat treatment (reflow process performed after laser marking) when a semiconductor package is mounted on a substrate (motherboard, etc.).

In addition, in the case of manufacturing a semiconductor chip with a protective film formed using the film for forming a protective film described in Patent Document 1, for example, as shown in FIG. 8, first, a film for forming a protective film on the back surface of the semiconductor wafer 9 (13) is affixed (Fig. 8(a)). Subsequently, after laser printing the protective film-forming film 13 (Fig. 8(b)), curing by heat or energy rays as necessary in order to increase the protective performance of the protective film-forming layer (Fig. 8(c)), After affixing the dicing tape, the semiconductor wafer is divided into chips by dicing and picked up. Subsequently, the semiconductor chip on which the picked up protective film is formed is subjected to a heat treatment (reflow process) when the semiconductor package is mounted on the substrate (Fig. 8(d)).

International Publication No. 2015/111632

In the conventional method for manufacturing a protective film-forming semiconductor chip using a protective film-forming film or a protective film-forming composite sheet, laser printing is performed on the protective film-forming film, and the curing process of the protective film-forming film or the semiconductor package is applied to the substrate. In the reflow process at the time of mounting, there was a concern that the laser printing would deteriorate. On the other hand, in the curing process or the reflow process of the film for protective film formation, a method of laser printing on the back surface of the semiconductor wafer can be considered so that the laser printing does not deteriorate.

For example, as shown in Fig. 9, first, after laser printing is performed on the back surface of the semiconductor wafer 9 (Fig. 9(a)), the protective film-forming film 13 is affixed to the printing surface (Fig. 9(b)). ). Subsequently, the protective film-forming film 13 is cured by heat or energy rays as necessary (Fig. 9(c)), and after affixing a dicing tape, the semiconductor wafer is divided into chips by dicing and picked up. do. Subsequently, the semiconductor chip on which the picked up protective film is formed is subjected to a heat treatment (reflow process) (Fig. 9(d)).

However, the conventional film for forming a protective film has a low visible light transmittance so as to enable printing by irradiation of laser light, and is not suitable for use in direct laser printing on the back surface of a semiconductor wafer because the printing is hidden.

The present invention has been made in view of the above circumstances, a film for forming a protective film that can be used for laser printing on the back surface of a semiconductor wafer and protecting the printing surface, and a composite sheet for forming a protective film having the same, and an inspection method and identification Provides a way.

In order to solve the above problems, the present invention provides the following.

[1] A film for forming a protective film, which is affixed on the back surface of a semiconductor wafer to be laser printed, and used for manufacturing a semiconductor chip on which a protective film is formed, wherein the film for forming a protective film having an image clarity of 110 or more.

[2] A composite sheet for forming a protective film, provided with a support sheet, and provided with the film for forming a protective film according to [1] on the support sheet.

[3] A step of laser printing on the back surface of a semiconductor wafer, a step of affixing the film for forming a protective film according to [1] to the back surface of the semiconductor wafer, and the back surface of the semiconductor wafer or obtained by separating the semiconductor wafer An inspection method comprising a step of inspecting the semiconductor wafer or the semiconductor chip over a protective film formed by attaching the protective film-forming film to the back surface of a semiconductor chip.

[4] In the step of inspecting, laser printing on the semiconductor wafer or the semiconductor chip over the protective film formed by attaching the protective film-forming film to the back surface of the semiconductor wafer or the semiconductor chip obtained by separating the semiconductor wafer into pieces. The inspection method according to the above [3], which is a step of inspecting the presence or absence of a printed print, a grinding mark on the back surface of the semiconductor wafer or the semiconductor chip, or a foreign material between the semiconductor wafer or the semiconductor chip and the protective film.

[5] The step of laser printing on the back surface of the semiconductor wafer, the step of attaching the film for forming a protective film according to the above [1] to the back surface of the semiconductor wafer, and the back surface of the semiconductor chip obtained by separating the semiconductor wafer. An identification method comprising a step of reading a laser-printed print on the semiconductor chip over a protective film formed by affixing a protective film-forming film and identifying the type of the semiconductor chip.

According to the present invention, a film for forming a protective film that can be used for laser printing on the back surface of a semiconductor wafer and protecting the printed surface, a composite sheet for forming a protective film having the same, and an inspection method and an identification method are provided.

1 is a cross-sectional view schematically showing a film for forming a protective film according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
4 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
5 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
7 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention.
8 is a cross-sectional view schematically showing a conventional manufacturing process of a semiconductor chip with a protective film formed thereon.
9 is a cross-sectional view schematically showing a method of using the film for forming a protective film according to an embodiment of the present invention.

◇ Film for forming a protective film

The film for forming a protective film of the present invention is a film for forming a protective film, which is affixed on a laser-printed back surface of a semiconductor wafer and used for manufacturing a semiconductor chip on which the protective film is formed, and has an image sharpness of 110 or more. The image sharpness of the film for forming a protective film is based on JIS K 7374, and the sum of the evaluation values measured using five types of slits (slit widths: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm) Say.

The image clarity of the film for forming a protective film is 110 or more, preferably 130 or more, more preferably 150 or more, and particularly preferably 170 or more. Since the image clarity of the protective film-forming film of the present invention is not less than the lower limit value, the image clarity of the protective film formed by attaching the protective film-forming film to the back surface of the semiconductor wafer is also good. The image clarity of the film for forming a protective film may be 500 or less, 450 or less, and 400 or less.

Since the image clarity of the film for forming a protective film of the present invention is good, the semiconductor wafer or the semiconductor over the protective film formed by attaching the protective film-forming film to the back surface of a semiconductor wafer or a semiconductor chip obtained by separating the semiconductor wafer into pieces You can inspect the chip. More specifically, letters, symbols, laser-printed on the semiconductor wafer or the semiconductor chip over the protective film formed by attaching the protective film-forming film to the back surface of the semiconductor wafer or the semiconductor chip obtained by separating the semiconductor wafer into pieces, Prints such as shape can be read, and the presence or absence of the print, grinding marks on the back surface of the semiconductor wafer or the semiconductor chip, or the presence or absence of foreign matter between the semiconductor wafer or the semiconductor chip and the protective film can be inspected. In addition, when there is a foreign substance, the state of the foreign substance may be inspected.

The image sharpness of the protective film-forming film can be adjusted by the components contained in the protective film-forming composition described later, and among them, fine adjustment is possible by selecting the type and size of the filler, and the type or content of the colorant.

The light transmittance of the film for forming a protective film at a wavelength of 550 nm is preferably 30% or more, more preferably 40% or more, and particularly preferably 45% or more. When the light transmittance of the protective film-forming film at a wavelength of 550 nm is equal to or greater than the lower limit, it becomes possible to more clearly read the prints such as laser-printed characters, symbols, and patterns. The light transmittance of the film for protective film formation at a wavelength of 550 nm may be 99.5% or less, or 99.0% or less. The light transmittance of the protective film-forming film at a wavelength of 550 nm can be adjusted by the components contained in the protective film-forming composition described later, particularly the thermosetting component, the type and content of the filler and/or colorant.

The haze of the film for forming a protective film is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 10 or less. When the haze of the protective film-forming film is equal to or less than the above upper limit, printing such as laser-printed characters, symbols, and patterns can be read more clearly. The haze of the film for forming a protective film may be 0.5 or more, or 1.0 or more. "Haze" means a value obtained by measuring according to JIS K 7136 unless otherwise noted. The haze of the protective film-forming film may be adjusted by the components contained in the protective film-forming composition described later, in particular, the type and content of the thermosetting component, filler and/or colorant, and the like, and may also be adjusted by the surface roughness of the film for forming a protective film.

The surface roughness of the film for forming a protective film is preferably 0.090 µm or less, and more preferably 0.070 µm or less. The surface roughness of the film for forming a protective film may be 0.009 µm or more, or 0.010 µm or more. When the surface roughness of the film for forming a protective film is equal to or less than the above upper limit, the visibility of printing such as laser-printed characters, symbols, and patterns is improved. In addition, in this specification, "surface roughness" means so-called arithmetic mean roughness calculated in conformity with JIS B 0601:2001, unless otherwise specified, and may be abbreviated as "Ra". The surface roughness of the protective film-forming film can be adjusted depending on the coating conditions and the components contained in the protective film-forming composition.

The film for forming a protective film may be cured by irradiation with energy rays or heat treatment to become a protective film. This protective film is for protecting the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer or semiconductor chip. The film for forming a protective film is soft and can be easily affixed to an object to be pasted. The energy ray-curable protective film-forming film can form a protective film by curing in a shorter time than the thermosetting protective film-forming film.

1 is a cross-sectional view schematically showing a film 13 for forming a protective film according to an embodiment of the present invention. Meanwhile, in the drawings used in the following description, in order to make it easier to understand the features of the present invention, there are cases in which parts that become main parts are enlarged for convenience, and the dimensional ratio of each component is not limited to the actual.

The protective film-forming film 13 shown here includes a first release film 151 on one surface (in this specification, it may be referred to as a “first surface”) 13a, and the first The second release film 152 is provided on the other surface (in this specification, it may be referred to as a "second surface") on the other surface opposite to the surface 13a.

Such a protective film-forming film 13 is preferable for storage in a roll shape, for example.

The film 13 for forming a protective film may have curability or may be non-curable without curability.

Moreover, when the film for protective film formation has curability, either of thermosetting property and energy ray curing property may be sufficient.

The film for forming a non-curable protective film can be formed using a composition for forming a non-curable protective film described later.

The film for thermosetting protective film formation can be formed using the composition for thermosetting protective film formation mentioned later.

The film for forming an energy ray-curable protective film can be formed using the composition for forming an energy ray-curable protective film described later.

Both the first release film 151 and the second release film 152 may be known.

The first peeling film 151 and the second peeling film 152 may be the same as each other, for example, even if the peeling force required for peeling from the protective film-forming film 13 is different from each other, etc. do.

In the protective film formation film 13 shown in FIG. 1, the back surface of a semiconductor wafer (not shown) is affixed to the exposed surface formed by removing either of the first release film 151 and the second release film 152. Then, the exposed surface formed by removing the other side of the first release film 151 and the second release film 152 becomes the affixed surface of the support sheet.

◇Composite sheet for forming a protective film

The composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet, and includes the film for forming a protective film on the support sheet.

In the present invention, even after the protective film-forming film is cured, as long as the laminated structure of the support sheet and the cured product of the protective film-forming film (that is, the support sheet and the protective film) is maintained, this laminated structure is referred to as ``composite for forming a protective film. It is called "sheet".

The thickness of the semiconductor wafer to be used for the composite sheet for forming a protective film of the present invention is not particularly limited, but it is preferably 30 to 1000 µm, and 30 to 400 µm, from the viewpoint of making the division of a semiconductor chip described later easier. It is more preferable.

Hereinafter, the configuration of the composite sheet for forming a protective film will be described in detail.

◎ Support sheet

The support sheet may be composed of one layer (single layer), or may be composed of a plurality of layers of two or more layers. When the support sheet is made of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effect of the present invention is not impaired. A dicing tape or an adhesive tape for semiconductor processing can be used.

Preferred supporting sheets include, for example, a base material provided, and a pressure-sensitive adhesive layer is directly contacted and laminated on the base material (the base material and the pressure-sensitive adhesive layer are in contact and laminated in this order); A substrate, an intermediate layer, and a pressure-sensitive adhesive layer, in this order, in contact with each other in the thickness direction and laminated; What consists only of a base material, etc. are mentioned.

Examples of the composite sheet for forming a protective film of the present invention will be described below for each type of such support sheet with reference to the drawings.

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

On the other hand, in the drawings after FIG. 2, the same components as those shown in the previously described drawings are denoted by the same reference numerals as those in the illustrated drawings, and detailed descriptions thereof will be omitted.

The protective film-forming composite sheet 1A shown here includes a substrate 11, a pressure-sensitive adhesive layer 12 on the substrate 11, and a protective film-forming film 13 on the pressure-sensitive adhesive layer 12. We have. The support sheet 10 is a laminate of the substrate 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1A for forming a protective film is, in other words, one surface of the support sheet 10 (in this specification, "the first It may be referred to as "surface") (10a) has a structure in which a film for forming a protective film 13 is laminated. Further, the protective film-forming composite sheet 1A further includes a release film 15 on the protective film-forming film 13.

In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one surface of the substrate 11 (in this specification, it may be referred to as a ``first surface'') 11a, and the adhesive layer One surface of (12) (in this specification, it may be referred to as a ``first surface'') A protective film-forming film 13 is laminated on the entire surface of 12a, and the protective film-forming film 13 is formed. A jig adhesive layer 16 is laminated on a part of the first surface 13a, that is, in an area near the periphery, and among the first surface 13a of the protective film forming film 13, the jig adhesive layer 16 is The release film 15 is laminated on the unlaminated surface and the surface 16a (upper surface and side surface) of the jig adhesive layer 16.

In the protective film-forming composite sheet 1A, the protective film-forming film 13 has an image sharpness of 110 or more.

The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or a multilayer structure in which layers containing an adhesive component are laminated on both surfaces of a sheet serving as a core material.

In the protective film-forming composite sheet 1A shown in FIG. 2, with the release film 15 removed, the back surface of a semiconductor wafer (not shown) is affixed to the first surface 13a of the protective film-forming film 13 , In addition, the upper surface of the surface 16a of the jig adhesive layer 16 is affixed to a jig such as a ring frame and used.

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

The protective film-forming composite sheet 1B shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 2 except that the jig adhesive layer 16 is not provided. That is, in the composite sheet 1B for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the entire surface of the first surface 12a of the pressure-sensitive adhesive layer 12 The protective film-forming film 13 is laminated, and the release film 15 is laminated on the entire surface of the first surface 13a of the protective film-forming film 13.

In the composite sheet 1B for forming a protective film, the film 13 for forming a protective film has an image sharpness of 110 or more.

The protective film-forming composite sheet 1B shown in FIG. 3 is a semiconductor wafer (not shown) in a part of the center side of the first surface 13a of the protective film-forming film 13 with the release film 15 removed. ) Is affixed, and a region near the periphery is further affixed to a jig such as a ring frame to be used.

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

The protective film-forming composite sheet 1C shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 2 except that the pressure-sensitive adhesive layer 12 is not provided. That is, in the composite sheet 1C for forming a protective film, the support sheet 10 is made of only the substrate 11. Then, a protective film-forming film 13 is laminated on the first surface 11a (the first surface 10a of the support sheet 10) of the substrate 11, and the first surface of the protective film-forming film 13 The jig adhesive layer 16 is laminated in a part of (13a), that is, in the region near the periphery, and among the first surface 13a of the protective film forming film 13, the jig adhesive layer 16 is laminated. The release film 15 is laminated on the non-existent region and the surface 16a (upper surface and side surface) of the jig adhesive layer 16.

In the protective film-forming composite sheet 1C, the protective film-forming film 13 has an image clarity of 110 or more.

The protective film-forming composite sheet 1C shown in FIG. 4 is similar to the protective film-forming composite sheet 1A shown in FIG. 2, with the release film 15 removed, the first of the protective film-forming film 13. The back surface of a semiconductor wafer (not shown) is affixed to the surface 13a, and the upper surface of the surface 16a of the adhesive layer 16 for a jig is affixed to a jig such as a ring frame to be used.

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

The protective film-forming composite sheet 1D shown here is the same as the protective film-forming composite sheet 1C shown in FIG. 4 except that the jig adhesive layer 16 is not provided. That is, in the protective film-forming composite sheet 1D, the protective film-forming film 13 is laminated on the first surface 11a of the substrate 11, and the first surface 13a of the protective film-forming film 13 The release film 15 is laminated on the entire surface of.

In the composite sheet 1D for forming a protective film, the film 13 for forming a protective film has an image sharpness of 110 or more.

The protective film-forming composite sheet 1D shown in FIG. 5 is similar to the protective film-forming composite sheet 1B shown in FIG. 3, with the release film 15 removed, the first of the protective film-forming film 13 Among the surfaces 13a, the rear surface of a semiconductor wafer (not shown) is affixed to a partial region on the center side, and a region near the periphery is further affixed to a jig such as a ring frame to be used.

6 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.

The protective film-forming composite sheet 1E shown here is the same as the protective film-forming composite sheet 1B shown in FIG. 3 except that the shape of the protective film-forming film is different. That is, the protective film-forming composite sheet 1E includes a substrate 11, an adhesive layer 12 on the substrate 11, and a protective film forming film 23 on the adhesive layer 12. It is done by doing. The support sheet 10 is a laminate of the substrate 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1E for forming a protective film is, in other words, for forming a protective film on the first surface 10a of the support sheet 10. The film 23 has a laminated configuration. Further, the protective film-forming composite sheet 1E further includes a release film 15 on the protective film-forming film 23.

In the composite sheet 1E for forming a protective film, the pressure-sensitive adhesive layer 12 is laminated on the first side 11a of the base material 11, and a part of the first side 12a of the pressure-sensitive adhesive layer 12, that is, the center A protective film-forming film 23 is laminated on the side region. And, of the first surface 12a of the pressure-sensitive adhesive layer 12, on a region in which the protective film-forming film 23 is not laminated and on the surface 23a (top and side surfaces) of the protective film-forming film 23 The release film 15 is laminated.

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

In the protective film-forming composite sheet 1E, the protective film-forming film 23 has an image clarity of 110 or more.

In the protective film-forming composite sheet 1E shown in FIG. 6, with the release film 15 removed, the back surface of a semiconductor wafer (not shown) is affixed to the surface 23a of the protective film-forming film 23, Of the first surface 12a of the low pressure-sensitive adhesive layer 12, a region in which the protective film-forming film 23 is not laminated is affixed to a jig such as a ring frame and used.

7 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to still another embodiment of the present invention.

The protective film-forming composite sheet 1F shown here is the same as that shown in Figs. 2 and 4 in a region of the first surface 12a of the pressure-sensitive adhesive layer 12 in which the protective film-forming film 23 is not laminated. It is the same as the protective film-forming composite sheet 1E shown in Fig. 6 except that the jig adhesive layer 16 is laminated. That is, the protective film-forming composite sheet 1F includes a substrate 11, an adhesive layer 12 on the substrate 11, and a protective film forming film 23 on the adhesive layer 12. And, of the first surface 12a of the pressure-sensitive adhesive layer 12, a jig adhesive layer 16 is laminated on a region in which the protective film-forming film 23 is not laminated. The support sheet 10 is a laminate of the substrate 11 and the pressure-sensitive adhesive layer 12, and the composite sheet 1F for forming a protective film is, in other words, for forming a protective film on the first surface 10a of the support sheet 10. The film 23 has a laminated configuration. Further, the protective film-forming composite sheet 1F further includes a release film 15 on the protective film-forming film 23.

In the composite sheet 1F for forming a protective film, the adhesive layer 12 is laminated on the first surface 11a of the substrate 11, and a part of the first surface 12a of the adhesive layer 12, that is, the center A protective film-forming film 23 is laminated on the side region. And, of the first surface 12a of the pressure-sensitive adhesive layer 12, on a region in which the protective film-forming film 23 is not laminated and on the surface 23a (top and side surfaces) of the protective film-forming film 23 The release film 15 is laminated.

When the protective film-forming composite sheet 1F is viewed in a plan view from above, the protective film-forming film 23 has a smaller surface area than the pressure-sensitive adhesive layer 12, and has, for example, a shape such as a circle shape.

In the composite sheet 1F for forming a protective film, the film 23 for forming a protective film has an image clarity of 110 or more.

In the protective film-forming composite sheet 1F shown in FIG. 7, with the release film 15 removed, the back surface of a semiconductor wafer (not shown) is affixed to the front surface 23a of the protective film-forming film 23, Among the surfaces 16a of the adhesive layer 16 for a log jig, the upper surface is affixed to a jig such as a ring frame and used.

As described above, the composite sheet for forming a protective film may have any form of the supporting sheet and the film for forming a protective film, or may be provided with an adhesive layer for a jig. However, as shown in Figs. 2 and 4, it is preferable that a jig adhesive layer is provided on the protective film forming film as the protective film-forming composite sheet provided with the jig adhesive layer.

The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to the ones shown in Figs. 2 to 7, and some configurations of the ones shown in Figs. 2 to 7 are changed within a range that does not impair the effects of the present invention. Alternatively, it may be deleted or another configuration may be added to the one described so far.

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

In addition, in the composite sheet for forming a protective film shown in FIGS. 2, 3, 6, and 7, an intermediate layer may be formed between the substrate 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by laminating a substrate, an intermediate layer, and an adhesive layer in this order in the thickness direction thereof. Here, the intermediate layer is the same as the intermediate layer which may be formed in the composite sheet for forming a protective film shown in FIGS. 4 and 5.

In addition, in the composite sheet for forming a protective film shown in FIGS. 2 to 7, layers other than the intermediate layer may be formed at arbitrary points.

In addition, in the composite sheet for forming a protective film, a partial gap may be formed between the release film and the layer in direct contact with the release film.

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

In the composite sheet for forming a protective film of the present invention, a layer in direct contact with the film for forming a protective film in a supporting sheet such as an adhesive layer may be non-energy ray curable or energy ray curable.

In the case of non-energy ray curing, the composite sheet for forming a protective film can be manufactured at a lower cost.

In the case of energy ray curing, the composite sheet for forming a protective film makes it easier to adjust the adhesive force, and it becomes easier to adjust the suitability of dicing or pick-up.

On the other hand, in the present invention, ``non-curing property'' means a property that does not cure by heating or irradiation of energy rays, etc., ``thermosetting property'' means a property that cures by heating, and ``energy ray curing property'' means energy It refers to the property of hardening by irradiating the line.

In the present invention, the "energy ray" means having both energy among electromagnetic waves or charged particle rays, and examples thereof include ultraviolet rays, radiation, and electron beams.

Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet source. The electron beam can be irradiated with what is generated by an electron beam accelerator or the like.

The support sheet may be transparent, may be opaque, and may be colored depending on the purpose.

When the film for forming a protective film has energy ray curing properties, it is preferable that the support sheet transmits energy rays.

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

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

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

When the transmittance of the light is within such a range, it is possible to read prints such as letters, symbols, and shapes laser-printed on the semiconductor wafer or the semiconductor chip through the protective film through the support sheet, and the print, the semiconductor wafer or The presence or absence of a grinding mark on the back surface of the semiconductor chip, a semiconductor wafer, or a foreign material between the semiconductor chip and the protective film may be inspected. In addition, if there is a foreign substance, the state of the foreign substance may be inspected.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 532 nm is not particularly limited, but it is possible to set it as 95%, for example.

In addition, in the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is within such a range, it is possible to read prints such as letters, symbols, and shapes laser-printed on the semiconductor wafer or the semiconductor chip through the protective film through the support sheet, and the print, the semiconductor wafer or The presence or absence of a grinding mark on the back surface of the semiconductor chip, a semiconductor wafer, or a foreign material between the semiconductor chip and the protective film may be inspected. In addition, if there is a foreign substance, the state of the foreign substance may be inspected.

On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 1064 nm is not particularly limited, but it is possible to set it as 95%, for example.

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

○ Description

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

Examples of the resin include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-norbornene copolymer (copolymers obtained using ethylene as a monomer); Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as a monomer); polystyrene; Polycycloolefin; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, and wholly aromatic polyesters in which all structural units have an aromatic cyclic group; A copolymer of two or more of the above polyesters; Poly(meth)acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone; Polyether ketone, etc. are mentioned.

Further, examples of the resin include polymer alloys such as a mixture of the polyester and other resins. It is preferable that the polymer alloy of the polyester and other resins has a relatively small amount of resin other than polyester.

In addition, as the resin, for example, a crosslinked resin in which one or two or more of the resins exemplified so far is crosslinked; Modified resins such as ionomers using one or two or more of the resins exemplified so far can also be mentioned.

In addition, in this specification, "(meth)acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid. For example, "(meth)acryloyl group" is a concept including both "acryloyl group" and "methacryloyl group", and "(meth)acrylic "Rate" is a concept including both "acrylate" and "methacrylate".

The number of resins constituting the substrate may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

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

Here, the "thickness of a base material" means the thickness of the entire base material, and for example, the thickness of a base material comprising a plurality of layers means the total thickness of all layers constituting the base material.

It is preferable that the substrate has high accuracy in thickness, that is, the variation in thickness is suppressed irrespective of the portion. Among the above-described constituent materials, examples of materials that can be used to construct a substrate having such a high precision of thickness include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like.

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 main constituent materials such as the resin.

It is preferable that the optical properties of the substrate satisfy the optical properties of the support sheet described above. That is, the base material may be transparent or opaque, may be colored depending on the purpose, or another layer may be deposited.

And, when the film for protective film formation has energy ray curability, it is preferable that the base material transmits energy rays.

In order to improve the adhesion with other layers such as an adhesive layer formed thereon, the substrate is uneven treatment by sand blast treatment, solvent treatment, etc., corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, The surface may be subjected to oxidation treatment such as flame treatment, chromic acid treatment, or hot air treatment.

In addition, the surface of the base material may have been subjected to a primer treatment.

In addition, the substrate may have an antistatic coat layer and a protective film-forming composite sheet overlapping each other and having a layer that prevents the substrate from adhering to another sheet, or a layer that prevents the substrate from adhering to the adsorption table.

Among these, the substrate is particularly preferably subjected to an electron beam irradiation treatment since the occurrence of fragments of the substrate due to friction of the blades during dicing is suppressed.

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

○Adhesive layer

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

Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferable.

On the other hand, in the present invention, "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness. For example, not only the resin itself has adhesiveness, but also other components such as additives and A resin exhibiting adhesiveness by combined use of, and a resin exhibiting adhesiveness by the presence of a trigger such as heat or water are also included.

The pressure-sensitive adhesive layer may consist of one layer (single layer), may consist of a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of these plurality of layers is specifically limited. It doesn't work.

The thickness of the pressure-sensitive adhesive layer is preferably 1 µm or more and 100 µm or less, more preferably 1 µm or more and 60 µm or less, and particularly preferably 1 µm or more and 30 µm or less.

Here, the "thickness of the adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer consisting of a plurality of layers means the total thickness of all the layers constituting the pressure-sensitive adhesive layer.

The optical properties of the pressure-sensitive adhesive layer may be set to satisfy the optical properties of the support sheet described above. That is, the pressure-sensitive adhesive layer may be transparent or may be colored depending on the purpose.

And, when the film for protective film formation has energy ray curability, it is preferable that the pressure-sensitive adhesive layer transmits energy rays.

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

<<adhesive composition>>

The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, by coating the pressure-sensitive adhesive composition on the surface to be formed of the pressure-sensitive adhesive layer and drying as necessary, the pressure-sensitive adhesive layer can be formed on a target site. In the pressure-sensitive adhesive composition, the content ratio between components that do not vaporize at room temperature is usually the same as the content ratio between the components in the pressure-sensitive adhesive layer. In this specification, the term "normal temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25°C.

Coating of the pressure-sensitive adhesive composition may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, a Mayer bar. The method of using various coaters, such as a coater and a kiss coater, is mentioned.

When forming a pressure-sensitive adhesive layer on a substrate, for example, the pressure-sensitive adhesive layer may be laminated on the substrate by coating the pressure-sensitive adhesive composition on the substrate and drying as necessary. In addition, in the case of forming an adhesive layer on a substrate, for example, by coating an adhesive composition on a release film and drying as necessary to form a pressure-sensitive adhesive layer on the release film, the exposed surface of the pressure-sensitive adhesive layer is described as a substrate. By bonding with one surface of, an adhesive layer may be laminated on the substrate.

When the pressure-sensitive adhesive layer is energy-ray-curable, the energy-ray-curable pressure-sensitive adhesive composition is, for example, a non-energy-ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”). And, the pressure-sensitive adhesive composition (I-1) containing an energy ray-curable compound; Containing an energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as ``adhesive resin (I-2a)'') Pressure-sensitive adhesive composition (I-2); The adhesive resin (I-2a) and the adhesive composition (I-3) containing an energy ray-curable compound, and the like can be mentioned.

When the pressure-sensitive adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable pressure-sensitive adhesive composition include a pressure-sensitive adhesive composition (I-4) containing the non-energy-ray-curable pressure-sensitive adhesive resin (I-1a).

[Adhesive resin (I-1a)]

The pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), the pressure-sensitive adhesive composition (I-3), and the pressure-sensitive adhesive composition (I-4) (hereinafter, encompassing these pressure-sensitive adhesive compositions, ``Adhesive composition (I-1) ) To (I-4)"), the adhesive resin (I-1a) is preferably an acrylic resin.

Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.

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

It is preferable that the said acrylic polymer further has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylate alkyl ester.

As the functional group-containing monomer, for example, the functional group becomes a starting point for crosslinking by reacting with a crosslinking agent described later, or the functional group reacts with an unsaturated group in an unsaturated group-containing compound described later, thereby introducing an unsaturated group into the side chain of the acrylic polymer What makes it possible is mentioned.

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

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

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

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

In the pressure-sensitive adhesive compositions (I-1) to (I-4), the constituent units of the acrylic resin, such as the acrylic polymer, may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof. Can be arbitrarily selected.

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass with respect to the total amount of the structural unit.

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

In the pressure-sensitive adhesive composition (I-1) or pressure-sensitive adhesive composition (I-4), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total mass of the pressure-sensitive adhesive composition (I-1) or the pressure-sensitive adhesive composition (I-4) is It is preferably 5 to 99% by mass.

[Adhesive resin (I-2a)]

The pressure-sensitive adhesive resin (I-2a) in the pressure-sensitive adhesive compositions (I-2) and (I-3) contains, for example, an unsaturated group having an energy ray-polymerizable unsaturated group in the functional group in the pressure-sensitive adhesive resin (I-1a). It is obtained by reacting a compound.

The unsaturated group-containing compound is a compound having a group capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group.

Examples of the energy ray-polymerizable unsaturated group include a (meth)acryloyl group, a vinyl group (ethenyl group), and an allyl group (2-propenyl group), and a (meth)acryloyl group is preferable.

Examples of groups that can be bonded to 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 hydroxyl groups and amino groups that can be bonded to carboxyl groups or epoxy groups.

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) or (I-3) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected. have.

In the adhesive composition (I-2) or (I-3), the ratio of the content of the adhesive resin (I-2a) to the total mass of the adhesive composition (I-2) or (I-3) is 5 to 99 mass It is preferably %.

[Energy ray curable compound]

Examples of the energy ray-curable compound in the pressure-sensitive adhesive compositions (I-1) and (I-3) include a monomer or oligomer that has an energy ray-polymerizable unsaturated group and can be cured by irradiation with energy rays.

Among the energy ray-curable compounds, monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Polyhydric (meth)acrylates such as 1,4-butylene glycol di(meth)acrylate and 1,6-hexanediol (meth)acrylate; Urethane (meth)acrylate; Polyester (meth)acrylate; Polyether (meth)acrylate; Epoxy (meth)acrylate, etc. are mentioned.

Among the energy ray-curable compounds, oligomers include, for example, oligomers obtained by polymerization of the monomers exemplified above.

The energy ray-curable compounds contained in the pressure-sensitive adhesive composition (I-1) or (I-3) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the energy ray-curable compound to the total mass of the pressure-sensitive adhesive composition (I-1) is preferably 1 to 95% by mass.

In the pressure-sensitive adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 400 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a).

[Crosslinking agent]

When using the above acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth)acrylate alkyl ester as the adhesive resin (I-1a), the pressure-sensitive adhesive composition (I-1), (I It is preferable that -3) or (I-4) further contains a crosslinking agent.

In addition, when using the acrylic polymer having structural units derived from the same functional group-containing monomer as in the adhesive resin (I-1a), for example, as the adhesive resin (I-2a), the adhesive composition (I-2) Silver may further contain a crosslinking agent.

The crosslinking agent in the adhesive resins (I-1a) and (I-2a) reacts with the functional group, for example, to crosslink the adhesive resins (I-1a) or the adhesive resins (I-2a). .

Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy-based crosslinking agents such as ethylene glycol glycidyl ether (crosslinking agents having a glycidyl group); Aziridine-based crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; Metal chelate-based crosslinking agents such as aluminum chelate (crosslinking agents having a metal chelate structure); Isocyanurate-based crosslinking agents (crosslinking agents having an isocyanuric acid skeleton), and the like.

The crosslinking agent contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), (I-3), or (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the content of the adhesive resin (I-1a). Do.

In the pressure-sensitive adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-2a).

[Photopolymerization initiator]

The pressure-sensitive adhesive compositions (I-1), (I-2), and (I-3) (hereinafter, these pressure-sensitive adhesive compositions are encompassed and abbreviated as “adhesive compositions (I-1) to (I-3)”) are And may further contain a photoinitiator. Even if the pressure-sensitive adhesive compositions (I-1) to (I-3) containing a photopolymerization initiator are irradiated with relatively low energy energy rays such as ultraviolet rays, the curing reaction sufficiently proceeds.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal. Phosphorus compounds; Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethan-1-one; Acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; Α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanocene; Thioxanthone compounds such as thioxanthone; Peroxide compounds; Diketone compounds such as diacetyl; benzyl; Dibenzyl; Benzophenone; 2,4-diethyl thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; And quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.

Further, as the photopolymerization initiator, for example, a photosensitizer such as amine may be used.

The photopolymerization initiators contained in the pressure-sensitive adhesive compositions (I-1) to (I-3) may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the photoinitiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound.

In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a).

In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound.

[Other additives]

The pressure-sensitive adhesive compositions (I-1) to (I-4) may contain other additives that do not correspond to any of the above-described components within a range that does not impair the effects of the present invention.

Examples of the above other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, coloring agents (pigments, dyes), sensitizers, tackifiers, reaction retardants, and crosslinking accelerators (catalysts ), and other known additives.

On the other hand, the reaction retarding agent is, for example, in the pressure-sensitive adhesive compositions (I-1) to (I-4) during storage by the action of the catalyst incorporated in the pressure-sensitive adhesive compositions (I-1) to (I-4). , It is to suppress the progress of the crosslinking reaction which is not intended. Examples of the reaction retarding agent include forming a chelate complex by chelate to a catalyst, and more specifically, one having two or more carbonyl groups (-C(=O)-) in one molecule. .

The other additives contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The content of the other additives in the pressure-sensitive adhesive compositions (I-1) to (I-4) is not particularly limited, and may be appropriately selected according to the kind.

[menstruum]

The pressure-sensitive adhesive compositions (I-1) to (I-4) may contain a solvent. When the pressure-sensitive adhesive compositions (I-1) to (I-4) contain a solvent, the application aptitude to the surface to be coated is improved.

The solvent is preferably an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; Esters such as ethyl acetate (carboxylic acid ester); Ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as cyclohexane and n-hexane; Aromatic hydrocarbons such as toluene and xylene; Alcohol, such as 1-propanol and 2-propanol, etc. are mentioned.

The number of solvents contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The content of the solvent in the pressure-sensitive adhesive compositions (I-1) to (I-4) is not particularly limited and may be appropriately adjusted.

○ Manufacturing method of adhesive composition

The pressure-sensitive adhesive compositions such as pressure-sensitive adhesive compositions (I-1) to (I-4) are obtained by blending the pressure-sensitive adhesive and, if necessary, each component for constituting the pressure-sensitive adhesive composition such as components other than the pressure-sensitive adhesive.

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

The method of mixing each component at the time of mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; Mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

○ Film for forming a thermosetting protective film

As a preferable film for thermosetting protective film formation, what contains a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) is a component that can be considered to be formed by a polymerization reaction of a polymerizable compound. In addition, the thermosetting component (B) is a component capable of curing reaction using heat as a trigger of the reaction. On the other hand, in the present invention, a polycondensation reaction is also included in the polymerization reaction.

The film for thermosetting protective film formation may consist of one layer (single layer), or may consist of a plurality of layers of two or more layers. When the film for thermosetting protective film formation consists of multiple layers, these multiple layers may be the same or different from each other. Here, "the multiple layers may be the same or different from each other" means the same as in the case of the above description. In addition, when a plurality of layers are different from each other, the combination of these plurality of layers is not particularly limited.

The thickness of the thermosetting protective film forming 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 thermosetting protective film-forming film is equal to or more than the above lower limit, when the thermosetting protective film-forming film is used as a protective film, a protective film having a higher protective ability can be formed. In addition, when the thickness of the thermosetting protective film-forming film is equal to or less than the above upper limit, excessive thickness is suppressed.

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 that the film for forming a thermosetting protective film is constituted. It means the total thickness of all layers.

The curing conditions at the time of affixing and curing the thermosetting protective film forming film on the back surface of the semiconductor wafer are not particularly limited as long as the curing degree is such that the protective film sufficiently exhibits its function, and depending on the type of the thermosetting protective film forming film, Choose appropriately.

For example, the heating temperature during curing of the thermosetting protective film-forming 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. Further, the heating time during the curing is preferably 0.5 hours or more and 5 hours or less, more preferably 0.5 hours or more and 3 hours or less, and particularly preferably 1 hour or more and 2 hours or less.

<<Composition for forming a 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. For example, by coating a composition for forming a thermosetting protective film on a surface to be formed of a film for forming a thermosetting protective film, and drying as necessary, a film for forming a thermosetting protective film can be formed at a target site. The ratio of the content 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 ratio of the content of the components of the film for forming a thermosetting protective film. Here, "room temperature" is as described above.

The coating of the composition for forming a thermosetting protective film can be performed, for example, in the same manner as in the case of coating of the pressure-sensitive adhesive composition described above.

Drying conditions of the composition for forming a thermosetting protective film are not particularly limited, but when the composition for forming a thermosetting protective film contains a solvent described below, it is preferable to heat-dry, in this case, for example, at 70°C or more and 130°C or less. It is preferable to dry under conditions of 10 seconds or more and 5 minutes or less.

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

As a composition for forming a thermosetting protective film, for example, a composition for forming a thermosetting protective film (III-1) containing a polymer component (A) and a thermosetting component (B) (in this specification, simply ``composition (III-1)'' It may be abbreviated as) and the like.

[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 composition (III-1) and the polymer component (A) contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

As the polymer component (A), for example, acrylic resin (resin having (meth)acryloyl group), polyester, urethane resin (resin having urethane bond), acrylic urethane resin, silicone resin (resin having siloxane bond) ), a rubber resin (a resin having a rubber structure), a phenoxy resin, a thermosetting polyimide, and the like, and an acrylic resin is preferable.

As said acrylic resin in polymer component (A), a well-known acrylic polymer is mentioned.

It is preferable that it is 10000 or more and 2000000 or less, and, as for the weight average molecular weight (Mw) of an acrylic resin, it is more preferable that it is 100000 or more and 1500000 or less. When the weight average molecular weight of the acrylic resin is more than the above lower limit, the handling property and shape stability (stability with time during storage) of the film for forming a thermosetting protective film are improved. In addition, when the weight average molecular weight of the acrylic resin is less than or equal to the above upper limit, the film for forming a thermosetting protective film is easier to follow on the uneven surface of the adherend, and the occurrence of voids between the adherend and the film for forming a thermosetting protective film is more suppressed. .

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

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C or more and 70°C or less, and more preferably -30°C or more and 50°C or less. When the Tg of the acrylic resin is equal to or greater than the above lower limit, the adhesive force between the protective film and the supporting sheet (adhesive layer) is suppressed, and the peelability of the supporting sheet is improved. Further, when the Tg of the acrylic resin is equal to or less than the above upper limit, the adhesion of the protective film to the adherend is improved.

Examples of the acrylic resin include polymers of one or two or more (meth)acrylic acid esters; And copolymers of two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.

Examples of the (meth)acrylic acid ester constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n- (meth)acrylate. Butyl, (meth) isobutyl acrylate, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate, pentyl (meth) acrylate, (meth) heptyl acrylate, (meth) acrylate 2-ethyl Hexyl, (meth) acrylate isooctyl, (meth) acrylate n-octyl, (meth) acrylate n-nonyl, (meth) acrylate isononyl, (meth) acrylate, (meth) acrylate, (meth) acrylate Dodecyl ((meth) acrylate lauryl), (meth) acrylate tridecyl, (meth) acrylate tetradecyl ((meth) acrylate myristylus), (meth) acrylate pentadecyl, (meth) acrylate hexadecyl ((meth) (Meth) acrylate alkyl ester in which the alkyl group constituting the alkyl ester such as palmityl acrylate), (meth) acrylate heptadecyl, and (meth) acrylate octadecyl ((meth) acrylate stearyl) has a chain structure having 1 to 18 carbon atoms ;

(Meth)acrylate cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;

(Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate;

(Meth) acrylate cycloalkenyl ester, such as (meth) acrylate dicyclopentenyl ester;

(Meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylate dicyclopentenyloxyethyl ester;

Imide (meth)acrylate;

Glycidyl group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate;

Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth) ) Hydroxyl group-containing (meth)acrylic acid esters such as 3-hydroxybutyl acrylic acid and 4-hydroxybutyl (meth)acrylate;

And substituted amino group-containing (meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylate. Here, the "substituted amino group" means a group obtained by substituting one or two hydrogen atoms of an amino group with a group other than a hydrogen atom.

The acrylic resin is, for example, in addition to the (meth)acrylic acid ester, one or two or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide. May be formed by copolymerization.

The number of monomers constituting the acrylic resin may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

In the present invention, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter, simply abbreviated as ``thermoplastic resin'' may be used alone) without using an acrylic resin, or an acrylic resin and You may use it together. By using the thermoplastic resin, the peelability of the protective film from the support sheet is improved, or the film for forming a thermosetting protective film is easily followed on the uneven surface of the adherend, and voids, etc. are generated between the adherend and the film for forming a thermosetting protective film. It may be suppressed more than this.

The weight average molecular weight of the thermoplastic resin is preferably 1000 or more and 100000 or less, and more preferably 3000 or more and 80000 or less. Here, the "weight average molecular weight" is as previously described.

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

Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the content of the polymer component (A) of the film for forming a thermosetting protective film) is the polymer component ( Regardless of the type of A), it is preferably 5% by mass or more and 85% by mass or less, and more preferably 5% by mass or more and 80% by mass or less.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is the polymer component (A) and the thermosetting component It is considered to contain (B).

[Thermosetting component (B)]

The thermosetting component (B) is a component for forming a hard protective film by curing the film for forming a thermosetting 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, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

Examples of the thermosetting component (B) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins, and epoxy-based thermosetting resins are preferred.

(Epoxy thermosetting resin)

The epoxy-based thermosetting resin consists of an epoxy resin (B1) and a thermosetting agent (B2).

The composition (III-1) and the epoxy-based thermosetting resin contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

Epoxy resin (B1)

Examples of the epoxy resin (B1) include known ones, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ethers and their hydrogenated products, orthocresol novolac epoxy resins, dicyclopenta Diene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher epoxy compounds.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. Epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. For this reason, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of a semiconductor chip with a protective film obtained using a composite sheet for forming a protective film is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by adding (meth)acrylic acid or a derivative thereof to an epoxy group.

In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring constituting the epoxy resin.

The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, (meth)acrylamide group, and the like. And an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but in terms of curability of the film for forming a thermosetting protective film, strength and heat resistance of the protective film after curing, it is preferably 300 or more and 30000 or less, and more preferably 300 or more and 10000 or less. And it is particularly preferably 300 or more and 3000 or less.

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

As for the epoxy resin (B1), 1 type may be used individually, 2 or more types may be used together, and when 2 or more types are used together, these combinations and ratios can be selected arbitrarily.

·Heat curing agent (B2)

The thermal curing agent (B2) functions as a curing agent for the epoxy resin (B1).

Examples of the thermosetting agent (B2) include a compound having two or more functional groups capable of reacting with an epoxy group per molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group in which an acid group is anhydride, and the like, and a phenolic hydroxyl group, an amino group, or an acid group is preferably an anhydride group. It is more preferable that it is a hydroxyl group or an amino group.

Among the thermal curing agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, aralkyl type phenol resins, and the like. I can.

Among the thermal curing agents (B2), examples of the amine curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”) and the like.

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

Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds obtained by substituting a part of the hydroxyl group of a phenol resin with a group having an unsaturated hydrocarbon group, and a compound obtained by directly bonding a group having an unsaturated hydrocarbon group to the aromatic ring of the phenol resin I can.

The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the above-described unsaturated hydrocarbon group.

When a phenolic curing agent is used as the thermal curing agent (B2), it is preferable that the thermal curing agent (B2) has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the supporting sheet.

Among the thermosetting agents (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 30000 or less, It is more preferable that it is 400 or more and 10000 or less, and it is especially preferable that it is 500 or more and 3000 or less.

Among the thermosetting agents (B2), for example, the molecular weight of the non-resin component such as biphenol and dicyandiamide is not particularly limited, but, for example, it is preferably 60 or more and 500 or less.

The thermosetting agent (B2) may be used singly or in combination of two or more, and when two or more of them are used in combination, combinations and ratios thereof 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 preferably 0.1 parts by mass or more and 500 parts by mass or less, based on 100 parts by mass of the epoxy resin (B1) content, and 1 mass. It is more preferable that it is at least 200 parts by mass. When the content of the thermosetting agent (B2) is equal to or greater than the lower limit, the curing of the film for forming a thermosetting protective film is more likely to proceed. Further, when the content of the thermosetting agent (B2) is equal to or less than the upper limit, the moisture absorption rate of the film for forming a thermosetting protective film is reduced, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is the polymer component (A). It is preferably 20 parts by mass or more and 500 parts by mass 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 with respect to 100 parts by mass of the content. When the content of the thermosetting component (B) is within such a range, the adhesive force between the protective film and the supporting sheet is suppressed, and the peelability of the supporting 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 curing accelerator (C) is a component for adjusting the curing rate of the composition (III-1).

Preferred curing accelerators (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 Imidazoles such as hydroxymethylimidazole (imidazole in which at least one hydrogen atom is substituted with a group other than a hydrogen atom); Organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphine in which at least one hydrogen atom is substituted with an organic group); Tetraphenyl boron salts, such as tetraphenyl phosphonium tetraphenyl borate and triphenyl phosphine tetraphenyl borate, etc. are mentioned.

The composition (III-1) and the curing accelerator (C) contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

When using a curing accelerator (C), in the composition (III-1) and the film for forming a thermosetting protective film, the content of the curing accelerator (C) is 0.01 parts by mass or more with respect to 100 parts by mass of the thermosetting component (B). It is preferably 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 7 parts by mass or less. When the content of the curing accelerator (C) is more than the lower limit, the effect of using the curing accelerator (C) is more remarkably obtained. In addition, when the content of the curing accelerator (C) is less than or equal to the above upper limit, for example, the high polarity curing accelerator (C) moves to the adhesive interface side with the adherend in the film for forming a thermosetting protective film under high temperature and high humidity conditions. The effect of suppressing segregation increases, and the reliability of the semiconductor chip with the protective film obtained by using the composite sheet for forming a 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). Since the film for forming a thermosetting protective film contains the filler (D), the protective film obtained by curing the film for forming a thermosetting protective film makes it easy to adjust the coefficient of thermal expansion, and by optimizing the coefficient of thermal expansion for the object to be formed, for forming a protective film. The reliability of the semiconductor chip with the protective film obtained by using the composite sheet is further improved. Further, when the film for forming a thermosetting protective film contains the filler (D), the moisture absorption rate of the protective film may be reduced or the heat dissipation property may be improved.

Although any of an organic filler and an inorganic filler may be sufficient as the filler (D), it is preferable that it is an inorganic filler.

Preferred inorganic fillers include powders such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide and boron nitride; Beads in which these inorganic fillers are spheroidized; Surface modified products of these inorganic fillers; Single crystal fibers of these inorganic fillers; Glass fiber, etc. are mentioned.

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

The average particle diameter of the filler (D) is preferably 10 µm or less. By setting it as the average particle diameter of 10 micrometers or less, it becomes easy to adjust the image sharpness of the film for protective film formation and a protective film to 110 or more. In order to further improve image clarity, the average particle diameter of the filler (D) is more preferably 6 µm or less.

When the filler is large, the image clarity tends to decrease, and even if the particle diameter is small, the clarity tends to decrease due to diffusion of light.

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

When using the filler (D), in the composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, the filler (D) of the film for forming a thermosetting protective film) Content) 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, and particularly preferably 15 parts by mass or more and 60% by mass or less. When the content of the filler (D) is within such a range, it becomes possible to manufacture a highly reliable chip by making it easier to adjust the thermal expansion coefficient, and to set the image sharpness to a desired range. In addition, when the filler (D) contains an amount exceeding 80% by mass, depending on the particle diameter of the filler (D), the image sharpness tends to decrease.

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

The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group of the polymer component (A), the thermosetting component (B), and the like, and more preferably a silane coupling agent.

Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropyltrimethoxysilane. Cidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-( 2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3 -Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltri Ethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc. are mentioned.

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

When a coupling agent (E) is used, in the composition (III-1) and the film for forming a thermosetting protective film, the content of the coupling agent (E) is 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B). Relatively, it is preferably 0.03 parts by mass or more and 20 parts by mass or less, more 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. When the content of the coupling agent (E) is equal to or greater than the lower limit, the use of the coupling agent (E), such as improving the dispersibility of the filler (D) in the resin, or improving the adhesion to the adherend of the film for forming a thermosetting protective film. The effect is obtained more remarkably. In addition, when the content of the coupling agent (E) is equal to or less than the upper limit, generation of outgas is further suppressed.

[Crosslinking agent (F)]

When using a polymer component (A) having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, which can be bonded to other compounds such as the acrylic resin described above, is used, the composition (III- 1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F) for crosslinking by bonding the functional group with another compound. By crosslinking using 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 an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate type crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine type crosslinking agent (a crosslinking agent having an aziridinyl group), and the like.

As the organic polyvalent isocyanate compound, for example, an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds may be included and abbreviated as "aromatic polyvalent isocyanate compound etc." in some cases); Trimers, isocyanurates, and adducts such as the above aromatic polyvalent isocyanate compounds; And a terminal isocyanate urethane prepolymer obtained by reacting the above aromatic polyvalent isocyanate compound and the like with a polyol compound. The ``adduct body'' is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, or an alicyclic polyvalent isocyanate compound, and a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. It means a reaction product of, and examples thereof include a xylylene diisocyanate adduct of trimethylolpropane described later, and the like. In addition, "terminal isocyanate urethane prepolymer" is as described above.

More specifically as said organic polyvalent isocyanate compound, For example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Compounds in which any one or two or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are added to all or part of the hydroxyl groups of polyols such as trimethylolpropane; Lysine diisocyanate, etc. are mentioned.

Examples of the organic polyvalent imine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinylpropionate, Tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxyamide)triethylene melamine, and the like.

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

The composition (III-1) and the crosslinking agent (F) contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the case of using the crosslinking agent (F), the content of the crosslinking agent (F) in the composition (III-1) is preferably 0.01 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the polymer component (A). It is more preferable that it is more than 10 mass parts by mass and it is especially preferable that it is 0.5 mass parts or more and 5 mass parts or less. When the content of the crosslinking agent (F) is more than the lower limit, the effect of using the crosslinking agent (F) is more remarkably obtained. Further, when the content of the crosslinking agent (F) is equal to or less than the upper limit, excessive use of the crosslinking agent (F) is suppressed.

[Energy ray curable resin (G)]

The composition (III-1) may contain an energy ray-curable resin (G). Since the film for thermosetting protective film formation contains an energy ray-curable resin (G), the characteristic can be changed by energy ray irradiation.

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

Examples of the energy ray-curable compound include a compound having at least one polymerizable double bond in the molecule, and an acrylate compound having a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, etc. Chain-type aliphatic skeleton-containing (meth)acrylate; Cyclic aliphatic skeleton-containing (meth)acrylates such as dicyclopentanyldi(meth)acrylate; Polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; Oligoester (meth)acrylate; Urethane (meth)acrylate oligomers; Epoxy modified (meth)acrylate; Polyether (meth)acrylate other than the polyalkylene glycol (meth)acrylate; Itaconic acid oligomer, etc. are mentioned.

The weight average molecular weight of the energy ray-curable compound is preferably 100 or more and 30000 or less, and more preferably 300 or more and 10000 or less. Here, the "weight average molecular weight" is as previously described.

The energy ray-curable compound used for polymerization may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The energy ray-curable resin (G) contained in the composition (III-1) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof 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 10% by mass or more and 85% by mass It is particularly preferable that it is less than or equal to %.

[Photopolymerization initiator (H)]

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

As the photoinitiator (H) in the composition (III-1), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin Benzoin compounds such as methyl benzoate and benzoin dimethyl ketal; Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethan-1-one; Acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; Α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanocene; Thioxanthone compounds such as thioxanthone; Peroxide compounds; Diketone compounds such as diacetyl; benzyl; Dibenzyl; Benzophenone; 2,4-diethyl thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 2-chloroanthraquinone, etc. are mentioned.

Further, examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; Photosensitizers, such as amine, etc. are also mentioned.

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

In the composition (III-1), the content of the photopolymerization initiator (H) is preferably 0.1 parts by mass or more and 20 parts by mass or less, and 1 parts by mass or more and 10 parts by mass based on 100 parts by mass of the content of the energy ray-curable resin (G). It is more preferable that it is less than a part, and it is especially preferable that it is 2 mass parts or more and 5 mass parts or less.

[Coloring agent (I)]

The composition (III-1) and the film for forming a thermosetting protective film may contain the coloring agent (I) within a range that does not impair the effect of the invention.

As the colorant (I), well-known things, such as an inorganic pigment, an organic pigment, and an organic dye, are mentioned, for example.

The organic pigments and organic dyes include, for example, an aminium pigment, a cyanine pigment, a merocyanine pigment, a chromonium pigment, a squarylium pigment, an azrenium pigment, a polymethine pigment, a naphthoquinone pigment. , Pyryllium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, Isoindolinone dye, quinophthalone dye, pyrrole dye, thioindigo dye, metal complex dye (metal complex dye), dithiol metal complex dye, indolephenol dye, triarylmethane dye, anthra And quinone-based dyes, naphthol-based dyes, azomethine-based dyes, benzimidazolone-based dyes, pyrantrone-based dyes, and srene-based dyes.

Examples of the 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 pigments). Tin oxide)-based pigments, ATO (antimony tin oxide)-based pigments, and the like.

The composition (III-1) and the colorant (I) contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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 colorant (I) in the film for forming a thermosetting protective film to adjust the light transmittance of the protective film, it is possible to adjust the printing visibility when laser printing is performed on the wafer. Further, by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film, the designability of the protective film can be improved or the grinding marks on the back surface of the semiconductor wafer can be made difficult to show. Taking these points into consideration, the ratio of the content of the colorant (I) to the total content of all components other than the solvent in the composition (III-1) (that is, the content of the colorant (I) of the film for forming a thermosetting protective film), It is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7.5% by mass or less, and particularly preferably 0.1% by mass or more and 5% by mass or less. When the content of the colorant (I) is more than the lower limit, the effect of using the colorant (I) is more remarkably obtained. Further, when the content of the colorant (I) is equal to or less than the upper limit, excessive decrease in light transmittance of the film for forming a thermosetting protective film is suppressed.

[Universal Additive (J)]

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

The general-purpose additive (J) may be a well-known one, may be arbitrarily selected according to the purpose, and is not particularly limited, but preferable examples include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, and the like.

The composition (III-1) and the general-purpose additive (J) contained in the film for forming a thermosetting protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

[menstruum]

It is preferable that the composition (III-1) further contains a solvent. The composition (III-1) containing a solvent becomes good in handleability.

The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; Alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; And amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.

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

The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the composition (III-1) can be more uniformly mixed.

<<The manufacturing method of the composition for thermosetting protective film formation>>

Compositions for forming a thermosetting protective film such as composition (III-1) are obtained by blending each component for constituting the composition.

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

In the case of using a solvent, it may be used by mixing the solvent with any of the components other than the solvent and diluting the component in advance. You may use it by mixing with these compounding components.

The method of mixing each component at the time of mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; Mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15°C or more and 30°C or less.

○ Energy ray-curable protective film formation 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 having adhesiveness, and more preferably uncured and having adhesiveness. Here, "energy rays" and "energy rays hardenability" are as described above.

The energy ray-curable protective film-forming film may be only one layer (single layer), or may be a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited. Does not.

The thickness of the energy ray-curable protective film-forming 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 energy ray-curable protective film-forming film is more than the above lower limit, a protective film having a higher protective ability can be formed when the energy-ray-curable protective film-forming film is used as a protective film. In addition, when the thickness of the energy ray-curable protective film-forming film is equal to or less than the above upper limit, excessive thickness is suppressed.

Here, the term "thickness of the film for forming an energy ray-curable protective film" means the thickness of the entire 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 a plurality of layers is energy ray-curable. It means the total thickness of all the layers constituting the film for forming a protective film.

The curing conditions for forming the protective film by attaching and curing the film for forming the energy ray-curable protective film on the back surface of the semiconductor wafer are not particularly limited as long as the degree of curing is such that the protective film sufficiently exhibits its function, and the energy ray-curable protective film It may be appropriately selected according to the type of the film for formation.

For example, it is preferable that the illuminance of the energy ray at the time of curing the energy ray-curable protective film-forming film is 120 mW/cm 2 or more and 280 mW/cm 2 or less. In addition, it is preferable that the amount of light of the energy ray at the time of curing is 200 mJ/cm 2 or more and 1000 mJ/cm 2 or less.

<<Composition for energy ray-curable protective film formation>>

The film for energy ray-curable protective film formation can be formed using the composition for energy ray-curable protective film formation containing the constituent material. For example, by applying the composition for forming an energy ray-curable protective film on the surface to be formed of the film for forming an energy ray-curable protective film, and drying it as necessary, a film for forming an energy ray-curable protective film can be formed on the target site. . The content ratio of 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 components in the film for forming an energy ray-curable protective film. Here, "room temperature" is as described above.

The coating of the composition for forming an energy ray-curable protective film can be performed, for example, in the same manner as in the case of coating of the pressure-sensitive adhesive composition described above.

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-dry, in this case, for example, 70° C. or higher. It is preferable to dry it under the conditions of 10 seconds or more and 5 minutes or less at 130 degreeC or less.

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

As a composition for forming an energy ray-curable protective film, for example, the composition (IV-1) for forming an energy ray-curable protective film containing the energy ray-curable component (a) (in this specification, simply ``composition (IV-1) It may be abbreviated as ") and the like.

[Energy ray curable component (a)]

The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is a component for forming a hard protective film after curing, as well as imparting film formation and flexibility to the film for forming an energy ray-curable protective film. .

Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group having a weight average molecular weight of 80000 or more and 2000000 or less, and a compound (a2) having an energy ray-curable group having a molecular weight of 100 or more and 80000 or less. .

The polymer (a1) may be at least partially crosslinked with a crosslinking agent or may not be crosslinked.

(Polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 or more and 2000000 or less)

Examples of the polymer (a1) having an energy ray-curable group having a weight average molecular weight of 80000 or more and 2000000 or less include an acrylic polymer (a11) having a functional group capable of reacting with a group of other compounds, and a group that reacts with the functional group and energy ray-curable. An acrylic resin (a1-1) obtained by reacting an energy ray-curable compound (a12) having an energy ray-curable group such as a bond can be mentioned.

Examples of the functional groups capable of reacting with groups of other compounds include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group obtained by substituting one or two hydrogen atoms of the amino group with a group other than a hydrogen atom), and an epoxy group. . However, in terms of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips, the functional group is preferably a group other than a carboxyl group.

Among these, it is preferable that the said functional group is a hydroxyl group.

・Acrylic polymer (a11) having a functional group

Examples of the acrylic polymer (a11) having a functional group include those obtained by copolymerization of an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to these monomers, a monomer other than an acrylic monomer ( A non-acrylic monomer) may be copolymerized.

Further, the acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method may be employed for the polymerization method.

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

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylate. )(Meth)acrylate hydroxyalkyl such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Non-(meth)acrylic unsaturated alcohols (unsaturated alcohols having no (meth)acryloyl skeleton), such as vinyl alcohol and allyl alcohol, may be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid and citraconic acid; Anhydrides of the ethylenically unsaturated dicarboxylic acids; (Meth)acrylic acid carboxyalkyl esters, such as 2-carboxyethyl methacrylate, etc. are mentioned.

The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer.

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

Examples of acrylic monomers having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. )Isobutyl acrylate, (meth)acrylic acid sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate pentyl, (meth) acrylate, heptyl (meth) acrylate, (meth) acrylate 2-ethylhexyl, (meth) ) Isooctyl acrylate, (meth) acrylate n-octyl, (meth) acrylate n-nonyl, (meth) acrylate isononyl, (meth) acrylate, (meth) acrylate undecyl, (meth) acrylate dodecyl (( Meth) lauryl acrylate), (meth) tridecyl acrylate, (meth) tetradecyl acrylate ((meth) myristyl acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate ((meth) palmityl acrylate) , (Meth)acrylic acid alkyl ester in which the alkyl group constituting the alkyl ester such as heptadecyl (meth)acrylate and octadecyl (meth)acrylate ((meth) acrylate stearyl) has a chain structure having 1 to 18 carbon atoms. have.

In addition, examples of the acrylic monomer not having the functional group include alkoxyalkyl groups such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate. Containing (meth)acrylic acid ester; (Meth)acrylic acid esters having an aromatic group, including (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; Non-crosslinkable (meth)acrylamide and derivatives thereof; And (meth)acrylic acid esters having non-crosslinkable tertiary amino groups such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.

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

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; Vinyl acetate; Styrene, etc. are mentioned.

The number of the non-acrylic monomers constituting the acrylic polymer (a11) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the constituent unit derived from the acrylic monomer having the functional group to the total amount of the constituent units constituting it is preferably 0.1 to 50% by mass, and 1 to It is more preferable that it is 40 mass %, and it is especially preferable that it is 3-30 mass %. When the ratio is within such a range, in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12), the content of the energy ray-curable group is determined by the curing of the protective film. The degree can be easily adjusted to a preferable range.

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

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

Energy ray-curable compound (a12)

The energy ray-curable compound (a12) is a group capable of reacting with a functional group of the acrylic polymer (a11), and preferably has one or two or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group, and the above It is more preferable to have an isocyanate group as a group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group readily reacts with this hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

It is preferable that the said energy ray-curable compound (a12) has 1 or more and 5 or less of said energy ray-curable groups in 1 molecule, and it is more preferable that it has 1 or more and 3 or less.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meth-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (Bisacryloyloxymethyl) ethyl isocyanate;

An acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or a polyisocyanate compound and hydroxyethyl (meth)acrylate;

And acryloyl monoisocyanate compounds obtained by reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate.

Among these, it is preferable that the said energy ray-curable compound (a12) is 2-methacryloyloxyethyl isocyanate.

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

In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is 20 mol% or more. It is preferably 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 content is within such a range, the adhesive strength of the protective film after curing becomes larger. On the other hand, when the energy ray-curable compound (a12) is a monofunctional compound (having one group per molecule), the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) is different. In the case of a functional compound (having two or more of the above groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000 or more and 2000000 or less, and more preferably 300000 or more and 1500000 or less.

Here, the "weight average molecular weight" is as previously described.

When the polymer (a1) is at least partially crosslinked with a crosslinking agent, the polymer (a1) does not correspond to any of the above-described monomers described as constituting the acrylic polymer (a11), and A monomer having a group reacting with a crosslinking agent may be polymerized and crosslinked in the group reacting with the crosslinking agent, or may be crosslinked in the group reacting with the functional group derived from the energy ray-curable compound (a12).

The polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

(Compound (a2) having an energy ray-curable group and a molecular weight of 100 or more and 80000 or less)

As the energy ray-curable group of the compound (a2) having an energy ray-curable group having a molecular weight of 100 or more and 80000 or less, a group containing an energy ray-curable double bond is exemplified, and preferable examples include a (meth)acryloyl group and a vinyl group. Can be lifted.

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

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

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth) Acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxy Diethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy )Phenyl]propane, tricyclodecanedimethanoldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi (Meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di (Meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, neopentyl glycol Difunctional (meth)acrylates such as di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acryloxypropane;

Tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone-modified tris(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri (Meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Polyfunctional (meth)acrylates such as poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate;

Polyfunctional (meth)acrylate oligomers, such as a urethane (meth)acrylate oligomer, etc. are mentioned.

Among the compounds (a2), as an epoxy resin having an energy ray-curable group and a phenolic resin having an energy ray-curable group, those described in paragraph 0043 of “JP 2013-194102 A” can be used. These resins also correspond to resins constituting the thermosetting component described later, but are handled as the compound (a2) in the present invention.

The compound (a2) preferably has a weight average molecular weight of 100 or more and 30000 or less, and more preferably 300 or more and 10000 or less.

Here, the "weight average molecular weight" is as previously described.

The compound (a2) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

[Polymer (b) not having an energy ray-curable group]

When the composition (IV-1) and the film for forming an energy ray-curable protective film contain the compound (a2) as the energy ray-curable component (a), a polymer (b) having no energy ray-curable group is also contained. desirable.

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

Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins.

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

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

Examples of the acrylic monomers constituting the acrylic polymer (b-1) include (meth)acrylate alkyl esters, (meth)acrylic acid esters having a cyclic skeleton, glycidyl group-containing (meth)acrylic acid esters, and hydroxyl group-containing ( Meth)acrylic acid ester, substituted amino group-containing (meth)acrylic acid ester, and the like. Here, the "substituted amino group" is as described above.

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

Examples of the (meth)acrylate ester having a cyclic skeleton include (meth)acrylate cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;

(Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate;

(Meth) acrylate cycloalkenyl ester, such as (meth) acrylate dicyclopentenyl ester;

Cycloalkenyloxyalkyl (meth)acrylates, such as dicyclopentenyloxyethyl (meth)acrylate, etc. are mentioned.

Examples of the glycidyl group-containing (meth)acrylic acid ester include glycidyl (meth)acrylate.

Examples of the hydroxyl group-containing (meth)acrylic acid ester include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxy (meth)acrylate. Propyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like.

Examples of the substituted amino group-containing (meth)acrylic acid ester include N-methylaminoethyl (meth)acrylate.

Examples of the non-acrylic monomers constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; Vinyl acetate; Styrene, etc. are mentioned.

The polymer (b) which does not have the energy ray-curable group at least partially cross-linked with a cross-linking agent includes, for example, a reactive functional group in the polymer (b) reacted with a cross-linking agent.

The reactive functional group may be appropriately selected depending on the type of crosslinking agent and the like, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. Further, when the crosslinking agent is an epoxy-based compound, examples of the reactive functional group include a carboxyl group, an amino group, and an amide group, and among these, a carboxyl group having high reactivity with an epoxy group is preferable. However, in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip, the reactive functional group is preferably a group other than a carboxyl group.

Examples of the polymer (b) having no energy ray-curable group having a reactive functional group include those obtained by polymerizing at least a monomer having the reactive functional group. In the case of the acrylic polymer (b-1), one having the above reactive functional group may be used as either or both of the above acrylic monomers and non-acrylic monomers as a monomer constituting it. For example, examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth)acrylic acid ester. In addition, in the above acrylic monomer or non-acrylic monomer, What is obtained by polymerizing a monomer obtained by substituting one or two or more hydrogen atoms with the above reactive functional groups is mentioned.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the constituent unit derived from the monomer having the reactive functional group to the total amount of the constituent units constituting it is preferably 1% by mass or more and 20% by mass or less. And it is more preferable that it is 2 mass% or more and 10 mass% or less. When the ratio is within such a range, in the polymer (b), the degree of crosslinking becomes a more preferable range.

The weight average molecular weight (Mw) of the polymer (b) not having an energy ray-curable group is preferably 10000 or more and 2000000 or less, and more preferably 100000 or more and 1500000 or less, from the viewpoint of better film-forming properties of the composition (IV-1). . Here, the "weight average molecular weight" is as previously described.

The composition (IV-1) and the energy ray-curable protective film-forming film contain only one type of polymer (b), which does not have an energy ray-curable group, and may be two or more types, and in the case of two or more types, combinations and ratios thereof Can be arbitrarily selected.

Examples of the composition (IV-1) include those containing either or both of the polymer (a1) and the compound (a2). In addition, when the composition (IV-1) contains the compound (a2), it is preferable to further contain a polymer (b) that does not have an energy ray-curable group, and in this case, further containing the above (a1) It is also desirable. Further, the composition (IV-1) does not contain the compound (a2), and may contain the polymer (a1) and the polymer (b) having no energy ray-curable group together.

When the composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, in the composition (IV-1), the compound (a2) The content is preferably 10 parts by mass or more and 400 parts by mass or less, more preferably 30 parts by mass or more and 350 parts by mass or less, based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) not having an energy ray-curable group. Do.

In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) not having an energy ray-curable group to the total content of components other than the solvent (that is, for forming an energy ray-curable protective film The total content of the energy ray-curable component (a) of the film and the polymer (b) having no energy ray-curable group) is preferably 5% by mass or more and 90% by mass or less, and more preferably 10% by mass or more and 80% by mass or less. And it is particularly preferably 20% by mass or more and 70% by mass or less. When the ratio of the content of the energy ray-curable component is within such a range, the energy ray-curable property of the film for forming an energy ray-curable protective film becomes better.

In addition to the energy ray-curable component, the composition (IV-1) contains one or two or more selected from the group consisting of a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general-purpose additive, depending on the purpose. You may have it. For example, the energy ray-curable protective film-forming film formed by using the composition (IV-1) containing the energy ray-curable component and the thermosetting component improves adhesion to an adherend by heating, and this energy ray The strength of the protective film formed from the film for forming a curable protective film is also improved.

As the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant, and general-purpose additive in the composition (IV-1), respectively, the thermosetting component (B) and the filler (D) in the composition (III-1) ), a coupling agent (E), a crosslinking agent (F), a photopolymerization initiator (H), a colorant (I), and the same as the general-purpose additive (J).

In the composition (IV-1), the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant, and general-purpose additive may each be used singly or in combination of two or more. When the above is used in combination, combinations and ratios thereof can be arbitrarily selected.

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

The composition (IV-1) preferably further contains a solvent from the viewpoint of improving its handling properties by dilution.

The solvent contained in the composition (IV-1) includes, for example, the same solvent as the solvent in the composition (III-1).

The number of solvents contained in the composition (IV-1) may be one or two or more.

<<The manufacturing method of the composition for energy ray-curable protective film formation>>

A composition for forming an energy ray-curable protective film such as composition (IV-1) is obtained by blending each component for constituting it.

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

In the case of using a solvent, it may be used by mixing the solvent with any of the components other than the solvent and diluting the component in advance. You may use it by mixing with these compounding components.

The method of mixing each component at the time of mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; Mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15°C or more and 30°C or less.

○ Film for forming a non-curable protective film

A preferable film for forming a non-curable protective film contains, for example, a non-curable component (c). In the film for forming a non-curable protective film, it is preferable that the non-curable component (c) does not have curability, but has an adhesive property to a support sheet and an appropriate hardness to protect a semiconductor wafer or chip. Here, "non-curable" is as described above.

The film for forming a non-curable protective film may be only one layer (single layer), or may be a plurality of layers of two or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not 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 equal to or greater than the lower limit, a protective film having a higher protective ability can be formed when the film for forming a non-curable protective film is used as a protective film. In addition, when the thickness of the film for forming a non-curable protective film is equal to or less than the above upper limit, excessive thickness is suppressed.

Here, the "thickness of the film for forming a non-curable protective film" means the thickness of the entire film for forming a non-curable protective film. For example, the thickness of the film for forming a non-curable protective film composed of a plurality of layers means a film for forming a non-curable protective film. Means the thickness of the sum of all the layers that make up it.

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

The film for forming a non-curable protective film can be formed using a composition for forming a non-curable protective film containing the constituent material. For example, by coating a composition for forming a non-curable protective film on a surface to be formed of a film for forming a non-curable protective film, and drying as necessary, a film for forming a non-curable protective film can be formed on a target site. The ratio of the content 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 ratio of the content of the components of the film for forming a non-curable protective film. Here, "room temperature" is as described above.

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

Drying conditions of the composition for forming a non-curable protective film are not particularly limited, but when the composition for forming a non-curable protective film contains a solvent to be described later, it is preferable to heat-dry, in this case, for example, 70° C. or more and 130° C. It is preferable to dry under the conditions of 10 seconds or more and 5 minutes or less below.

<Composition for forming a 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 (V-1) containing the non-curable component (c) (in this specification, simply abbreviated as ``composition (V-1)''). There are cases), etc. are mentioned.

Examples of the non-curable component (c) include, but are not limited to, acrylic polymers.

In addition to the non-curable component (c), the composition (V-1) may contain one or two or more selected from the group consisting of a filler, a coupling agent, a crosslinking agent, a colorant, and a general-purpose additive, depending on the purpose.

As the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive in the composition (V-1), the filler (D), coupling agent (E), and crosslinking agent (F) in the composition (III-1), respectively. , The colorant (I), and the same thing as the general-purpose additive (J) can be mentioned.

In the composition (V-1), the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive may each be used singly or in combination of two or more, and when two or more are used in combination, These combinations and ratios can be arbitrarily selected.

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

The composition (V-1) preferably further contains a solvent from the viewpoint of improving its handling properties by dilution.

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

The number of solvents contained in the composition (V-1) may be one or two or more.

<<The manufacturing method of the composition for forming a non-curable protective film>>

A composition for forming a non-curable protective film such as composition (V-1) is obtained by blending each component for constituting it.

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

In the case of using a solvent, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance. You may use it by mixing.

The method of mixing each component at the time of mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; Mixing using a mixer; What is necessary is just to select suitably from well-known methods, such as a method of adding ultrasonic waves and mixing.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15°C or more and 30°C or less.

◇Method of manufacturing a composite sheet for forming a protective film

The composite sheet for forming a protective film is ordered to be a ratio of the positional relationship of each layer described above, and the width (maximum length in the TD direction) of the protective film forming film to the width (maximum length in the TD direction) of the support sheet described above. It can be manufactured by laminating it as it is. The method of forming each layer is as described above.

For example, when manufacturing a composite sheet for forming a protective film, when the film for forming a protective film is additionally laminated on the pressure-sensitive adhesive layer laminated on the substrate, a composition for forming a thermosetting protective film on the pressure-sensitive adhesive layer, forming an energy ray-curable protective film It is possible to directly form a protective film-forming film by coating the composition for use or the composition for forming a non-curable protective film. In this way, in the case of forming a continuous two-layer laminated structure using any one composition, it is possible to form a new layer by further coating the composition on the layer formed from the composition. However, among these two layers, the layer to be laminated later is formed in advance using the composition on another release film, and the exposed side of the formed layer opposite to the side in contact with the release film is the exposed side of the other already formed layer. By bonding with, it is preferable to form a continuous two-layer laminated structure. At this time, it is preferable to apply the composition to the peeling-treated surface of the peeling film. The release film may be removed as necessary after formation of the laminated structure.

That is, in the case of manufacturing a composite sheet for forming a protective film, the pressure-sensitive adhesive composition is coated on the substrate and dried as necessary, so that the pressure-sensitive adhesive layer is laminated on the substrate, and separately, the composition for forming a thermosetting protective film on the release film, energy By coating a composition for forming a pre-curable protective film or a composition for forming a non-curable protective film and drying as necessary, a film for forming a protective film is formed on the release film, and the exposed surface of the film for forming a protective film is laminated on the substrate. By bonding with the exposed surface of the pressure-sensitive adhesive layer and laminating the film for protective film formation on the pressure-sensitive adhesive layer, a composite sheet for protective film formation is obtained.

On the other hand, in the case of laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, coating the pressure-sensitive adhesive composition on the release film and drying as necessary, on the release film. A pressure-sensitive adhesive layer may be laminated on the substrate by forming an adhesive layer and bonding the exposed surface of the pressure-sensitive adhesive layer to one surface of the substrate.

In either method, the release film may be removed at an arbitrary timing after forming the target laminated structure.

In this way, all layers other than the base material constituting the protective film-forming composite sheet (adhesive layer, protective film-forming film) can be formed in advance on the release film and laminated by a method of bonding to the surface of the target layer. , If necessary, a layer employing such a process may be appropriately selected to produce a composite sheet for forming a protective film.

On the other hand, the composite sheet for forming a protective film is usually stored in a state in which a release film is adhered to the surface of the outermost layer (for example, a film for forming a protective film) on the opposite side of the supporting sheet. Therefore, for forming a layer constituting the outermost layer, such as a composition for forming a thermosetting protective film, a composition for forming an energy ray-curable protective film, or a composition for forming a non-curable protective film, on this release film (preferably the peeling treatment surface thereof) By coating the composition and drying as necessary, a layer constituting the outermost layer is formed on the release film, and the remaining layers are formed on the exposed side opposite to the side in contact with the release film of this layer. The composite sheet for forming a protective film is also obtained by laminating in a state in which the release film is not removed and the film is bonded.

◇How to use the film for forming a protective film

The film for forming a protective film of the present invention can be used, for example, in a method for manufacturing a semiconductor chip with a protective film as described below or a method for manufacturing a semiconductor package.

That is, the protective film forming film is affixed to the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface) (Fig. 9(b)). At this time, laser printing may be performed on the back surface of the semiconductor wafer in advance (Fig. 9(a)), or laser printing may be performed on the back surface of the semiconductor wafer over the composite sheet for forming a protective film.

Subsequently, heating or energy rays are irradiated to the film for protective film formation as needed, and the film for protective film formation is hardened (FIG. 9(c)), and it is set as a protective film. Alternatively, in the case of a film for forming a protective film formed of a composition for forming a non-curable protective film, it may be used as a protective film in an uncured state. By laser printing on the back surface of the semiconductor wafer instead of laser printing on the protective film-forming film, even when the protective film-forming film is cured and used as a protective film, there is no fear of printing deterioration.

Next, a dicing tape is affixed to the protective film, and the semiconductor wafer is divided into a protective film to obtain a semiconductor chip. Then, the semiconductor chip is expanded by applying force from the side of the substrate while the protective film is affixed thereon (i.e., as a semiconductor chip with the protective film), and the cuff width between the semiconductor chips is widened, and then separated from the support sheet and picked up. do.

Next, the semiconductor chip with the obtained protective film formed thereon is flip-chip-connected to the circuit surface of the substrate, and then subjected to heat treatment (reflow process) to obtain a semiconductor package (Fig. 9(d)). Then, using this semiconductor package, an intended semiconductor device may be fabricated. By not performing laser printing on the film for forming a protective film, but laser printing on the back surface of the semiconductor wafer, the printing deterioration can be avoided even in heat treatment (reflow step).

On the other hand, in the case of curing the protective film-forming film by heating or irradiating energy rays, the timing may be before dicing or after dicing, as described above. Among them, it is preferable that the timing of curing the protective film-forming film by heating or irradiating energy rays is before dicing.

◇How to use the composite sheet for forming a protective film

The composite sheet for forming a protective film of the present invention can be used, for example, in a method for manufacturing a semiconductor chip with a protective film as described below or a method for manufacturing a semiconductor package.

That is, the protective film-forming composite sheet is affixed to the back surface of the semiconductor wafer (the surface opposite to the electrode-forming surface) by the protective film-forming film. At this time, laser printing may be performed on the back surface of the semiconductor wafer in advance, or laser printing may be performed on the back surface of the semiconductor wafer over the composite sheet for forming a protective film.

Subsequently, the film for forming a protective film is irradiated with heating or energy rays as necessary, and the film for forming a protective film is cured to obtain a protective film. Alternatively, in the case of a film for forming a protective film formed of a composition for forming a non-curable protective film, it may be used as a protective film without curing.

Next, the semiconductor wafer is divided into a protective film by dicing to obtain a semiconductor chip. The protective film forming film can be cured by laser printing on the back surface of the semiconductor wafer rather than laser printing on the protective film forming film, so that there is no fear of printing deterioration even when the protective film is formed.

Thereafter, the semiconductor chip is separated from the support sheet and picked up in the same manner as the method of using the protective film forming film. Next, the semiconductor chip with the obtained protective film formed thereon is flip-chip-connected to the circuit surface of the substrate, and then subjected to heat treatment (reflow step) to obtain a semiconductor package. Then, using this semiconductor package, an intended semiconductor device may be fabricated. By not performing laser printing on the film for forming a protective film, but laser printing on the back surface of the semiconductor wafer, the printing deterioration can be avoided even in heat treatment (reflow step).

When the film for forming a protective film is cured by heating or irradiating energy rays, the timing may be before dicing or after dicing, as described above. Among them, it is preferable that the timing of curing the protective film-forming film by heating or irradiating energy rays is before dicing.

◇Inspection method

The inspection method of the present invention includes a step of laser printing on the back surface of a semiconductor wafer, a step of attaching the protective film-forming film to the back surface of the semiconductor wafer, and a semiconductor chip obtained by separating the back surface of the semiconductor wafer or the semiconductor wafer into pieces. A step of inspecting the semiconductor wafer or the semiconductor chip over the protective film formed by attaching the protective film-forming film to the rear surface of the film is provided.

The inspection step includes laser-printed printing on the semiconductor wafer or the semiconductor chip over a protective film formed by affixing the protective film-forming film to the back surface of the semiconductor wafer or the semiconductor chip obtained by dividing the semiconductor wafer into pieces, It may be a step of inspecting the presence or absence of a grinding mark on the back surface of the semiconductor wafer or the semiconductor chip, or the presence or absence of a foreign material between the semiconductor wafer or the semiconductor chip and the protective film.

The inspection method of the present invention includes a step of laser printing on the back surface of a semiconductor wafer, a step of attaching a protective film forming film to the back surface of the semiconductor wafer, and a protective film formed by attaching the protective film forming film to the back surface of the semiconductor wafer. A step of inspecting laser-printed printing on the semiconductor wafer may be provided, a step of laser printing on the back surface of the semiconductor wafer, a step of attaching a protective film forming film to the back surface of the semiconductor wafer, and A step of inspecting the grinding marks on the back surface of the semiconductor wafer over the protective film formed by affixing the protective film forming film on the back surface may be provided, a step of laser printing on the back surface of the semiconductor wafer, and a protective film on the back surface of the semiconductor wafer A step of attaching a forming film, and a step of inspecting the presence or absence of a foreign substance between the semiconductor wafer and the protective film over the protective film formed by attaching the protective film forming film to the back surface of the semiconductor wafer.

In addition, the inspection method of the present invention includes a step of laser printing on the back surface of a semiconductor wafer, a step of affixing a film for forming a protective film on the back surface of the semiconductor wafer, and the protective film on the back surface of a semiconductor chip obtained by separating the semiconductor wafer. A process of inspecting laser-printed printing on the semiconductor chip over the protective film formed by affixing the forming film may be provided, a process of laser printing on the back surface of the semiconductor wafer, and a film for forming a protective film on the back surface of the semiconductor wafer. It may include a step of sticking and a step of inspecting the grinding marks on the back surface of the semiconductor chip over the protective film formed by attaching the protective film-forming film to the back surface of the semiconductor chip obtained by separating the semiconductor wafer. The process of laser printing on the back surface of the semiconductor wafer, a step of attaching a film for forming a protective film to the back surface of the semiconductor wafer, and the film for forming a protective film on the back surface of a semiconductor chip obtained by separating the semiconductor wafer into pieces. It may be provided with a step of inspecting the presence or absence of foreign substances between the semiconductor chip and the protective film.

◇How to identify

The identification method of the present invention includes a step of laser printing on the back surface of a semiconductor wafer, a step of attaching a film for forming a protective film on the back surface of the semiconductor wafer, and a step of forming the protective film on the back surface of a semiconductor chip obtained by separating the semiconductor wafer. And a step of reading a laser-printed print on the semiconductor chip over a protective film formed by affixing a film to identify the type of the semiconductor chip.

Example

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

Components used in the preparation of the protective film-forming composition (III-1) are shown below.

·Polymer component

(A)-1: 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)

(A)-2: An acrylic polymer obtained by copolymerizing 13 parts by mass of butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate, and 12 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight : 420,000)

·Thermosetting component

(B1)-1: Bisphenol A type epoxy resin (Mitsubishi Chemical JER828, epoxy equivalent 184 to 194 g/eq)

(B1)-2: Bisphenol A type epoxy resin (Mitsubishi Chemical JER1055, epoxy equivalent 800 to 900 g/eq)

(B1)-3: Dicyclopentadiene-type epoxy resin (Epiclon HP-7200HH manufactured by DIC Corporation, epoxy equivalent 255 to 260 g/eq)

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

·Hardening accelerator

(C)-1: 2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemical Industry Co., Ltd. Cuazole 2PHZ)

·filling

(D)-1: Silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 µm)

(D)-2: Silica filler (manufactured by Tatsumori, SV-10, average particle diameter 8.0 µm)

·Coupling agent

(E)-1: Silane coupling agent (A-1110 manufactured by Unicar, Japan)

·coloring agent

(I)-1: Organic black pigment (6377 black manufactured by Dainichi Seika Co., Ltd.)

(I)-2: Carbon black (manufactured by Mitsubishi Chemical, #MA650, average particle diameter 28 nm)

[Example 1]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (1))

By 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 (2.4 parts by mass), curing accelerator (C)-1 (2.4 parts by mass), filler (D)-1 (320 parts by mass), coupling agent (E)-1 (2 parts by mass) , And the coloring agent (I)-1 (15 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain a composition (1) for forming a thermosetting protective film.

(Production of protective film formation film (1))

On the release-treated side of a release film (“SP-PET381031,” manufactured by Lintec Co., Ltd., thickness 38 μm), in which one side of the polyethylene terephthalate film was peeled off by silicone treatment, the composition (1) for forming a protective film obtained above was added It applied with a knife coater and dried at 100 degreeC for 2 minutes, and the 25 micrometers-thick film for thermosetting protective film formation (1) was produced.

<Evaluation of film for protective film formation>

(Evaluation of image sharpness)

The sum of five types of slits (slit widths: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm) in accordance with JIS K 7374 using the Suga Testing Machine Co., Ltd. filamentity measuring instrument "ICM-10P" The value was measured as the image sharpness of the film for protective film formation (1). Table 1 shows the measurement results.

(Light transmittance of the film for forming a protective film at a wavelength of 550 nm)

Using a spectrophotometer (manufactured by SHIMADZU, UV-VIS-NIR SPECTROPHOTOMETER UV-3600), the light transmittance of the film for forming a protective film at a wavelength of 550 nm was measured. Table 1 shows the measurement results.

(Haze of protective film formation film)

For the film for forming a protective film, according to JIS K 7136:2000, NDH5000 (manufactured by Nippon Electric Co., Ltd.) was used, and a white LED (5V, 3W) was used as a light source, and the haze (%) was measured. Table 1 shows the measurement results.

(Surface roughness of the film for forming a protective film)

Using an optical interference type surface shape measuring device (manufactured by Veeco Metrology Group, product name "WYKO WT1100"), 10 times the magnification in PSI mode, the surface roughness (Ra) of the film for forming a protective film was measured in plane by 10 points, and the average value Saved. Table 1 shows the measurement results.

(Factor visibility evaluation)

Printing was performed on an 8-inch semiconductor wafer using a laser printing device CSM300M manufactured by EO Technics, and the film 1 for forming a protective film was affixed to the surface. The size of the laser-printed character was set to 0.3 mm×0.2 mm.

When the laser-printed character was visually observed over the protective film-forming film 1, it was determined whether or not the character could be visually recognized. Table 1 shows the evaluation results.

A: Clearly visible B: Slightly faint, but visible C: Not visible

(Evaluation of the reliability of the protective film)

The laminate obtained above was unscrewed, one of the peeling films was removed from one side of the film for forming a protective film, and a tape mounter (Lintec Co., Ltd.) on the polished surface of a #2000 polished silicon wafer (200 mm diameter, 280 μm thick) Using the production "Adwill RAD-3600F/12), the exposed surface of the protective film-forming film provided with the release film on one side was affixed while heating at 70°C. Subsequently, by irradiating ultraviolet rays under conditions of an illuminance of 230 mW/cm 2 and an amount of light of 170 mJ/cm 2, the film for forming a protective film was cured to form a protective film on the polished surface of the silicon wafer.

Next, after removing the other release film from the protective film, a dicing sheet ("Adwill G-562" manufactured by Lintec Corporation) was affixed, and the protective film was formed using a dicing device ("DFD651" manufactured by Disco Corporation). The formed silicon wafer was diced into a size of 3 mm x 3 mm to obtain a semiconductor chip with a protective film formed thereon.

Next, the semiconductor chip with the protective film obtained above was placed in the precondition shown below, which mimics the process when the semiconductor chip is mounted. That is, after baking the semiconductor chip with the protective film at 125°C for 20 hours, it was subjected to moisture absorption under conditions of 85°C and 85% relative humidity for 168 hours, and then the semiconductor chip with the protective film formed immediately after being removed from the moisture absorption environment was preheated at 160°C. , And passed three times through an IR reflow furnace at a peak temperature of 260°C. Then, the semiconductor chips with 25 protective films subjected to the operation up to this point were put into a cold and thermal shock device ("TSE-11-A" manufactured by ESPEC), held at -65°C for 10 minutes, and then maintained at 150°C for 10 minutes. The cooling cycle was repeated 1000 times.

Next, the semiconductor chip on which all the protective films were formed was taken out from the cold and thermal shock device, and the presence or absence of a lift or peeling in the junction of the semiconductor chip and the protective film, and the presence or absence of cracks in the semiconductor chip, was determined by a scanning ultrasonic imaging device (manufactured by Sonoscan ``D9600''). ^TM CSAM") was used to confirm by observing the cross section of the semiconductor chip on which the protective film was formed. Then, the number of semiconductor chips with a protective film in which at least one of the above-described lifting, peeling and cracking occurs is counted, and the case where the number (the number of NGs) is 2 or less is judged as a reliability pass (A), and is 3 or more. The case was determined as reliability failure (B). Table 1 shows the results.

[Example 2]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (2))

In the preparation of the composition (1) for forming a protective film of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass) was added to (D)-2: silica Except having changed to the filler (manufactured by Tatsumori, SV-10, average particle diameter of 8.0 µm) (320 parts by mass), it carried out similarly to Example 1, and obtained the composition (2) for thermosetting protective film formation.

(Production of protective film formation film (2))

In the production of the film for forming a protective film of Example 1, except having changed the composition for forming a protective film (1) to the composition for forming a protective film (2), it was carried out in the same manner as in Example 1 to obtain a film for forming a protective film (2). .

<Evaluation of film for protective film formation>

Using the same method as in Example 1, image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness and printing visibility, and reliability of the protective film of the protective film-forming film 2 were evaluated. The results are shown in Table 1 below. Example 1, which had a small filler diameter, had a large image clarity value and was excellent in visibility.

[Example 3]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (4))

In the preparation of the composition (1) for forming a protective film of Example 1, (I)-1: Example 1 except that an organic black pigment (CF3-4 manufactured by Dainichi Seika Industrial Co., Ltd.) (15 parts by mass) was not used. In the same manner as, a composition for forming a thermosetting protective film (4) was obtained.

(Production of protective film formation film (4))

In the production of the film for forming a protective film of Example 1, except having changed the composition for forming a protective film (1) to the composition for forming a protective film (4), in the same manner as in Example 1, a film for forming a protective film (4) was obtained. .

<Evaluation of film for protective film formation>

Using the same method as in Example 1, image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness and printing visibility, and reliability of the protective film of the protective film-forming film 4 were evaluated. The results are shown in Table 2 below.

[Comparative Example 1]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (5))

In the preparation of the composition (1) for forming a protective film of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 µm) (320 parts by mass) was added to (D)-3: silica It was changed to a filler (SC2050MA manufactured by Admatex, average particle diameter 8.0 µm) (320 parts by mass), and (I)-1: organic black pigment (CF3-4 manufactured by Daiichi Seika Co., Ltd.) (15 parts by mass) was added to (I) )-3: Carbon black (made by Mitsubishi Chemical Co., Ltd., #MA650, average particle diameter: 28 nm) Except having changed to (5.0 mass parts), it carried out similarly to Example 1, and obtained the composition for thermosetting protective film formation (5).

(Production of protective film formation film (5))

In the production of the film for forming a protective film of Example 1, except having changed the composition for forming a protective film (1) to the composition for forming a protective film (5), it was carried out in the same manner as in Example 1 to obtain a film for forming a protective film (5). .

<Evaluation of film for protective film formation>

Using the same method as in Example 1, image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness and printing visibility, and reliability of the protective film of the protective film-forming film 4 were evaluated. The results are shown in Table 2 below.

[Comparative Example 2]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (6))

In the preparation of the composition (1) for forming a protective film of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass) was added to (D)-2: silica Changed to filler (Tatsumori Co., SV-10, average particle diameter 8.0 µm) (320 parts by mass), and (I)-1: Organic black pigment (Cf3-4 manufactured by Daiichi Seika Co., Ltd.) (15 parts by mass) In the same manner as in Example 1, except for changing to (I)-3: carbon black (manufactured by Mitsubishi Chemical, #MA650, average particle diameter of 28 nm) (10.0 parts by mass), the composition for forming a thermosetting protective film (6) Got it.

(Production of protective film forming film (6))

In the production of the film for forming a protective film of Example 1, except having changed the composition for forming the protective film (1) to the composition for forming a protective film (6), it was carried out in the same manner as in Example 1 to obtain a film for forming a protective film (6). .

<Evaluation of film for protective film formation>

Using the same method as in Example 1, image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness and printing visibility, and reliability of the protective film of the protective film-forming film 6 were evaluated. The results are shown in Table 2 below.

[Example 4]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (7))

In the preparation of the composition (1) for forming a protective film of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass) was added to (D)-1: silica A composition (7) for forming a thermosetting protective film was obtained in the same manner as in Example 1, except that the filler (SC2050MA manufactured by Admatex, average particle diameter: 0.5 µm) (10 parts by mass) was changed.

(Production of protective film formation film (7))

In the preparation of the film for forming a protective film of Example 1, except having changed the composition for forming a protective film (1) to the composition for forming a protective film (7), it was carried out in the same manner as in Example 1 to obtain a film for forming a protective film (7). .

<Evaluation of film for protective film formation>

Using the same method as in Example 1, the image clarity of the film 7 for forming a protective film, light transmittance at a wavelength of 550 nm, haze, surface roughness and printing visibility, and reliability of the protective film were evaluated. The results are shown in Table 3 below.

[Example 5]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (8))

In the preparation of the composition (1) for forming a protective film of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass) was added to (D)-1: silica It was changed to a filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 µm) (10 parts by mass), and (I)-1: organic black pigment (6377 black manufactured by Daiichi Seika Co., Ltd.) (15 parts by mass) was not used. Except that, it carried out similarly to Example 1, and obtained the composition for thermosetting protective film formation (8).

(Production of protective film forming film (8))

In the production of the film for forming a protective film of Example 1, except having changed the composition for forming a protective film (1) to the composition for forming a protective film (8), in the same manner as in Example 1, a film for forming a protective film (8) was obtained. .

<Evaluation of film for protective film formation>

Using the same method as in Example 1, the image clarity of the protective film-forming film 8, the light transmittance at a wavelength of 550 nm, haze, surface roughness and printing visibility, and the reliability of the protective film were evaluated. The results are shown in Table 3 below.

[Example 6]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (9))

In the preparation of the composition (1) for forming a protective film of Example 1, (I)-1: organic black pigment (6377 black manufactured by Daiichi Seika Industrial Co., Ltd.) (15 parts by mass) was added to (I)-1: organic black pigment ( The composition for thermosetting protective film formation (9) was obtained like Example 1 except having changed it to 6377 black manufactured by Daiichi Seika Co., Ltd.) (32 parts by mass).

(Production of protective film formation film (9))

In the production of the film for forming a protective film of Example 1, except having changed the composition for forming a protective film (1) to the composition for forming a protective film (9), in the same manner as in Example 1, a film for forming a protective film (9) was obtained. .

<Evaluation of film for protective film formation>

Using the same method as in Example 1, image clarity, light transmittance at a wavelength of 550 nm, haze, surface roughness and printing visibility, and reliability of the protective film of the protective film-forming film 9 were evaluated. The results are shown in Table 3 below.

[Example 7]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (10))

In the preparation of the composition (1) for forming a protective film of Example 1, the acrylic polymer (weight average molecular weight: 370,000) (150 parts by mass) of (A)-1 was added to the acrylic polymer (weight average molecular weight) of (A)-2. : 420,000) Except having changed to (150 mass parts), it carried out similarly to Example 1, and obtained the composition for thermosetting protective film formation (10).

(Production of protective film forming film 10)

In the production of the film for forming a protective film of Example 1, except having changed the composition for forming a protective film (1) to the composition for forming a protective film (10), it was carried out in the same manner as in Example 1 to obtain a film for forming a protective film (10). .

<Evaluation of film for protective film formation>

Using the same method as in Example 1, the image clarity of the film 10 for forming a protective film, light transmittance at a wavelength of 550 nm, haze, surface roughness and printing visibility, and reliability of the protective film were evaluated. The results are shown in Table 4 below.

[Comparative Example 3]

<Production of film for protective film formation>

(Preparation of the composition for forming a protective film (11))

In the preparation of the composition (1) for forming a protective film of Example 1, (D)-1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass) was added to (D)-2: silica Filler (manufactured by Tatsumori, SV-10, average particle diameter 8.0 µm) (320 parts by mass), and (I)-1: organic black pigment (6377 black manufactured by Daiichi Seika Co., Ltd.) (15 parts by mass) (I)-1: A composition for forming a thermosetting protective film (11) was obtained in the same manner as in Example 1 except that it was changed to an organic black pigment (6377 black manufactured by Daiichi Seika Co., Ltd.) (32 parts by mass).

(Manufacture of protective film forming film 11)

In the preparation of the film for forming a protective film of Example 1, except having changed the composition for forming a protective film (1) to the composition for forming a protective film (11), it was carried out in the same manner as in Example 1 to obtain a film for forming a protective film (11). .

<Evaluation of film for protective film formation>

Using the same method as in Example 1, the image clarity of the film 11 for forming a protective film, light transmittance at a wavelength of 550 nm, haze, surface roughness and printing visibility, and reliability of the protective film were evaluated. The results are shown in Table 4 below.

From Tables 1 to 4, when the image clarity of the film for forming a protective film was 110 or more, it became clear that printing visibility was good.

The film for forming a protective film of the present invention is directly affixed to a semiconductor wafer and used for manufacturing a semiconductor device, and can be used for manufacturing a semiconductor device as a composite sheet for forming a protective film affixed to a supporting sheet such as a dicing tape.

Since the image clarity of the film for forming a protective film of the present invention is 110 or more, the printing visibility is good.Therefore, the film for forming a protective film is affixed to the back surface of a semiconductor wafer or a semiconductor chip obtained by separating the semiconductor wafer. The semiconductor wafer or the semiconductor chip can be preferably inspected.

In addition, since the image clarity of the film for forming a protective film of the present invention is 110 or more, the printing visibility is good. Therefore, a laser on the semiconductor chip through the protective film formed by affixing the protective film-forming film on the back surface of the semiconductor chip obtained by separating the semiconductor wafer By reading the printed factor, the type of the semiconductor chip can be preferably identified.

1A, 1B, 1C, 1D, 1E, 1F... Composite sheet for forming a protective film, 10... Support sheet, 10a... Surface of the supporting sheet (first surface), 11... Substrate, 11a... The surface of the substrate (the first side), 12... Pressure-sensitive adhesive layer, 12a... Surface of the pressure-sensitive adhesive layer (first surface), 13, 23... Film for forming a protective film, 13a, 23a... Surface (first surface) of the film for forming a protective film, 13b... Surface of the film for forming a protective film (second surface), 15... Release film, 151... 1st peeling film, 152... 2nd peeling film, 16... Jig adhesive layer, 16a... Surface of the jig adhesive layer, 9... Semiconductor wafer

Claims (5)

A film for forming a protective film, which is affixed on a back surface of a semiconductor wafer to be laser printed, and used for manufacturing a semiconductor chip on which a protective film is formed, wherein the film for forming a protective film having an image clarity of 110 or more. A composite sheet for forming a protective film, provided with a support sheet, and provided with the film for forming a protective film of claim 1 on the support sheet. A step of laser printing on the back surface of a semiconductor wafer, a step of affixing the film for forming a protective film of claim 1 on the back surface of the semiconductor wafer, and on the back surface of the semiconductor wafer or on the back surface of a semiconductor chip obtained by separating the semiconductor wafer, An inspection method comprising a step of inspecting the semiconductor wafer or the semiconductor chip over the protective film formed by attaching the protective film-forming film. The method of claim 3,
In the step of inspecting, a laser-printed print on the semiconductor wafer or the semiconductor chip over the protective film formed by attaching the protective film-forming film to the back surface of the semiconductor wafer or the semiconductor chip obtained by separating the semiconductor wafer into pieces, An inspection method comprising a step of inspecting the presence or absence of a grinding mark on the back surface of the semiconductor wafer or the semiconductor chip, or the presence or absence of a foreign material between the semiconductor wafer or the semiconductor chip and the protective film. A step of laser printing on the back surface of a semiconductor wafer, a step of affixing the film for forming a protective film of claim 1 on the back surface of the semiconductor wafer, and a step of affixing the film for forming a protective film on the back surface of a semiconductor chip obtained by separating the semiconductor wafer And a step of reading a laser-printed print on the semiconductor chip over the thus formed protective film to identify the type of the semiconductor chip.

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