JP6686241B1 - 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 definition of 110 or more, a protective film-forming composite sheet including the film (13), and an inspection method and an identification method. The protective film-forming film (13) of the present invention is attached to the laser-printed back surface of a semiconductor wafer and used for manufacturing a semiconductor chip with a protective film.

Description

The present invention relates to a protective film-forming film, a protective film-forming composite sheet, an inspection method and an identification method.
The present application claims priority based on Japanese Patent Application No. 2018-169591 filed in Japan on September 11, 2018, the contents of which are incorporated herein by reference.

  2. Description of the Related Art In recent years, semiconductor devices have been manufactured using a mounting method called a so-called face down method. In the face-down method, a semiconductor chip having electrodes such as bumps on the circuit surface is used, and the electrodes are bonded to the substrate. Therefore, the back surface of the semiconductor chip opposite to the circuit formation surface may be exposed.

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

  To form such a protective film, for example, a protective film-forming composite sheet comprising a protective film-forming film for forming a protective film on a support sheet is used. The protective film forming film can form a protective film by curing. Further, the support sheet can be used for fixing the semiconductor wafer when the semiconductor wafer having the protective film forming film or the protective film on the back surface is divided into semiconductor chips. Further, the support sheet can also be used as a dicing sheet, and the protective film-forming composite sheet can also be used as an integrated body of the protective film-forming film and the dicing sheet (for example, patents Reference 1.).

  The protective film forming film 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. As a result, it is possible to perform a printing process by irradiating a laser beam, and it is possible to inspect by infrared rays such as cracks existing in a work or a work obtained by processing the work.

  When manufacturing a semiconductor chip with a protective film using the protective film forming composite sheet provided with the protective film forming film described in Patent Document 1, for example, first, the protective film forming composite sheet is attached to the back surface of a semiconductor wafer. To do. Then, after laser-printing on the protective film forming film, in order to enhance the protective performance of the protective film forming layer, if necessary, through curing with heat or energy rays, the semiconductor wafer is divided into chips by dicing and picked up. To do. Next, the picked-up semiconductor film with a protective film is usually subjected to a heat treatment (a reflow step performed after laser marking) when the semiconductor package is mounted on a substrate (such as a mother board).

  Further, in the case of manufacturing a semiconductor chip with a protective film using the protective film forming film described in Patent Document 1, for example, as shown in FIG. The film 13 is attached (FIG. 8A). Then, after laser-printing on the protective film forming film 13 (FIG. 8 (b)), in order to enhance the protective performance of the protective film forming layer, it is optionally cured by heat or energy rays (FIG. 8 ( c)), After attaching the dicing tape, the semiconductor wafer is divided into chips by dicing and picked up. Next, the picked up semiconductor film with a protective film is subjected to a heat treatment (reflow step) when the semiconductor package is mounted on the substrate (FIG. 8D).

International Publication No. 2015/111632

  In the method for producing a protective film-coated semiconductor chip using a conventional protective film-forming film or a protective film-forming composite sheet, laser printing is performed on the protective film-forming film, or a curing step of the protective film-forming film, or, In the reflow process when mounting the semiconductor package on the substrate, laser printing may be deteriorated. On the other hand, a method of laser-printing on the back surface of the semiconductor wafer can be considered so that the laser-printing does not deteriorate in the curing step of the protective film forming film or the reflow step.

  For example, as shown in FIG. 9, laser printing is first performed on the back surface of the semiconductor wafer 9 (FIG. 9A), and then the protective film forming film 13 is attached to the printing surface (FIG. 9B). Next, the protective film forming film 13 is optionally cured by heat or energy rays (FIG. 9C), a dicing tape is attached, and then the semiconductor wafer is divided into chips by dicing and picked up. Next, the picked-up semiconductor film with the protective film is subjected to heat treatment (reflow step) (FIG. 9D).

  However, the conventional protective film forming film has a low visible light transmittance so that it can be printed by irradiation with a laser beam, and the printing is hidden in the application of laser printing directly on the back surface of the semiconductor wafer. It was not suitable because it would end up.

  The present invention has been made in view of the above circumstances, and a protective film forming film that can be used for laser printing on the back surface of a semiconductor wafer to protect the printed surface, and a protective film forming film including the same A composite sheet, and an inspection method and an identification method are provided.

In order to solve the above problems, the present invention provides the following.
[1] A protective film-forming film which is attached to a laser-printed back surface of a semiconductor wafer and is used for manufacturing a semiconductor chip with a protective film, and which has an image definition of 110 or more.
[2] A composite sheet for forming a protective film, comprising a supporting sheet, and the film for forming a protective film according to the above [1] on the supporting sheet.
[3] A step of laser-printing on the back surface of the semiconductor wafer, a step of attaching the protective film-forming film according to [1] to the back surface of the semiconductor wafer, and a back surface of the semiconductor wafer or the semiconductor wafer And a step of inspecting the semiconductor wafer or the semiconductor chip through the protective film formed by adhering the protective film forming film on the back surface of the obtained semiconductor chip.
[4] In the step of inspecting, through the protective film formed by affixing the protective film-forming film on the back surface of the semiconductor wafer or the back surface of a semiconductor chip obtained by dividing the semiconductor wafer into individual pieces, Laser marking on the semiconductor wafer or the semiconductor chip, inspecting the back surface of the semiconductor wafer or the semiconductor chip for grinding marks, or the presence or absence of foreign matter between the semiconductor wafer or the semiconductor chip and the protective film The inspection method according to [3] above.
[5] A step of laser-printing on the back surface of the semiconductor wafer, a step of pasting the protective film-forming film according to [1] on the back surface of the semiconductor wafer, and a semiconductor obtained by dividing the semiconductor wafer into pieces. A step of reading a laser-printed print on the semiconductor chip through the protective film formed by adhering the protective film-forming film on the back surface of the chip to identify the type of the semiconductor chip.

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

It is sectional drawing which shows the film for protective film formation which concerns on one Embodiment of this invention typically. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the manufacturing process of the conventional semiconductor chip with a protective film. It is sectional drawing which shows typically the usage method of the film for protective film formation which concerns on one Embodiment of this invention.

◇ Protective Film Forming Film The protective film forming film of the present invention is a protective film forming film which is affixed to the laser-printed back surface of a semiconductor wafer and is used in the production of a semiconductor chip with a protective film, and has an image clarity. Is 110 or more. The image clarity of the film for forming a protective film is measured using five kinds of slits (slit widths: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm and 2 mm) based on JIS K 7374. It means the total value.

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

  Due to the good image definition of the protective film forming film of the present invention, the protective film forming film is attached to the back surface of a semiconductor wafer or the back surface of a semiconductor chip obtained by dividing the semiconductor wafer into pieces. The semiconductor wafer or the semiconductor chip can be inspected through the protective film thus formed. More specifically, on the back surface of a semiconductor wafer or the back surface of a semiconductor chip obtained by dividing the semiconductor wafer into pieces, through the protection film formed by adhering the protection film forming film, the semiconductor wafer or Characters, symbols, patterns, etc. laser-printed on the semiconductor chip can be read, and the marking, grinding marks on the back surface of the semiconductor wafer or the semiconductor chip, or the semiconductor wafer or the semiconductor chip and the protective film. It is possible to inspect for foreign matter between If there is a foreign substance, the state of the foreign substance can be inspected.

  The image clarity of the film for forming a protective film can be adjusted by the components contained in the composition for forming a protective film to be described later, and among them, the kind and size of the filler and the kind and content of the colorant should be selected. This enables finer adjustments.

  The light transmittance at a wavelength of 550 nm of the protective film-forming film 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 higher than the lower limit value, it becomes possible to more clearly read the laser-printed characters, symbols, patterns and the like. The light transmittance of the protective film forming film at a wavelength of 550 nm may be 99.5% or less, or 99.0% or less. The light transmittance at a wavelength of 550 nm of the protective film-forming film should be adjusted by the components contained in the protective film-forming composition described below, particularly the type and content of the thermosetting component, the filler and / or the colorant. You can

  The haze of the protective film-forming film is preferably 40 or less, more preferably 30 or less, further 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, it becomes possible to more clearly read laser-printed characters, symbols, patterns and the like. The haze of the protective film forming film may be 0.5 or more, or 1.0 or more. The “haze” means a value obtained by measurement according to JIS K 7136, unless otherwise specified. The haze of the protective film-forming film can be adjusted by the components contained in the protective film-forming composition described below, particularly the type and content of the thermosetting component, the filler and / or the colorant, and the like. It can also be adjusted by the surface roughness of the forming film.

  The surface roughness of the protective film forming film is preferably 0.090 μm or less, and more preferably 0.070 μm or less. The surface roughness of the protective film forming film may be 0.009 μm or more, and may be 0.010 μm or more. When the surface roughness of the protective film forming film is not more than the upper limit value, the visibility of laser-printed characters, symbols, patterns and the like is improved. In the present specification, the term “surface roughness” means so-called arithmetic average roughness, which is determined in accordance with JIS B0601: 2001, and may be abbreviated as “Ra” unless otherwise specified. The surface roughness of the protective film forming film can be adjusted by the coating conditions and the components contained in the protective film forming composition.

  The protective film-forming film may be one that is cured by irradiation with energy rays or heat treatment to form 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 the semiconductor chip. The protective film forming film is soft and can be easily attached to an object to be attached. The energy ray curable protective film forming film can form the protective film by curing in a shorter time than the thermosetting protective film forming film.

  FIG. 1 is a sectional view schematically showing a protective film forming film 13 according to an embodiment of the present invention. Note that, in the drawings used in the following description, in order to facilitate understanding of the features of the present invention, for the sake of convenience, there may be a case where an essential part is enlarged and shown, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

The protective film forming film 13 shown here is provided with a first release film 151 on one surface (which may be referred to as “first surface” in the present specification) 13a of the film 13 and is provided with the first surface 13a. Is provided with the second release film 152 on the other surface (may be referred to as “second surface” in the present specification) 13b on the opposite side.
Such a protective film forming film 13 is suitable for storage, for example, as a roll.

The protective film forming film 13 may have curability or may be non-curable and not curable.
When the protective film forming film has curability, it may be either thermosetting or energy ray curable.
The non-curable protective film-forming film can be formed using the non-curable protective film-forming composition described below.
The thermosetting protective film-forming film can be formed using the thermosetting protective film-forming composition described below.
The energy ray-curable protective film-forming film can be formed using the energy ray-curable protective film-forming composition described below.

Both the first release film 151 and the second release film 152 may be known ones.
The first release film 151 and the second release film 152 may be the same as each other, or different from each other, for example, different release forces required when peeling from the protective film forming film 13. May be.

  In the protective film forming film 13 shown in FIG. 1, one of the first peeling film 151 and the second peeling film 152 is removed, and the back surface of the semiconductor wafer (not shown) is attached to the exposed surface. Then, the other remaining ones of the first release film 151 and the second release film 152 are removed, and the resulting exposed surface becomes the attachment surface of the support sheet.

◇ Composite sheet for protective film formation
A composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet, and the protective film forming 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 cured product of the support sheet and the protective film forming film (in other words, the support sheet and the protective film) is maintained, This laminated structure is referred to as a "composite sheet for forming a protective film".

The thickness of the semiconductor wafer to be used for the protective film-forming composite sheet of the present invention is not particularly limited, but is preferably 30 to 1000 μm in terms of easier division into semiconductor chips described later, More preferably, it is 30 to 400 μm.
Hereinafter, the structure 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 two or more layers. When the support sheet is 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 as long as the effects of the present invention are not impaired. A dicing tape or an adhesive tape for semiconductor processing can be diverted.

A preferred support sheet includes, for example, a base material and a pressure-sensitive adhesive layer laminated directly on the base material (a base material and a pressure-sensitive adhesive layer contacted and laminated in this order). A base material, an intermediate layer, and a pressure-sensitive adhesive layer, which are laminated in this order in contact with each other in the thickness direction; and a base material alone.
An example 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.

FIG. 2 is a cross-sectional view schematically showing a protective film-forming composite sheet according to an embodiment of the present invention.
2 and subsequent figures, the same components as those shown in the already described figures are given the same reference numerals as those in the already described figures, and the detailed description thereof will be omitted.

  The composite film 1A for forming a protective film shown here includes a base material 11, an adhesive layer 12 on the base material 11, and a protective film forming film 13 on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12, and the protective film-forming composite sheet 1A is, in other words, one surface of the support sheet 10 (in the present specification, "first surface"). (It may be called) 10a, and the film 13 for protective film formation is laminated | stacked. The protective film-forming composite sheet 1A further includes a release film 15 on the protective film-forming film 13.

  In the protective film-forming composite sheet 1 </ b> A, the pressure-sensitive adhesive layer 12 is laminated on one surface (may be referred to as “first surface” in this specification) 11 a of the base material 11 to form the pressure-sensitive adhesive layer 12. A protective film forming film 13 is laminated on the entire surface of one surface (sometimes referred to as “first surface” in the present specification) 12a, and a part of the first surface 13a of the protective film forming film 13 is formed. That is, the jig adhesive layer 16 is laminated in a region near the peripheral portion, and the surface of the first film 13a of the protective film forming film 13 on which the jig adhesive layer 16 is not laminated and the jig The release film 15 is laminated on the surface 16 a (upper surface and side surface) of the adhesive layer 16 for use.

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

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

  In the protective film forming composite sheet 1A shown in FIG. 2, the back surface of the semiconductor wafer (not shown) is attached to the first surface 13a of the protective film forming film 13 in a state where the release film 15 is removed. The upper surface of the surface 16a of the adhesive layer 16 for tools is attached to a jig such as a ring frame for use.

FIG. 3 is a cross-sectional view schematically showing a protective film-forming composite sheet 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 protective film-forming composite sheet 1B, the adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film forming film 13 is laminated on the entire first surface 12a of the adhesive layer 12. The release film 15 is laminated on the entire first surface 13a of the protective film forming film 13.

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

  The protective film-forming composite sheet 1B shown in FIG. 3 is a semiconductor wafer (not shown) in a partial region on the center side of the first surface 13a of the protective film-forming film 13 with the release film 15 removed. The back surface of () is attached, and the region near the peripheral portion is further attached to a jig such as a ring frame for use.

FIG. 4 is a cross-sectional view schematically showing a protective film-forming composite sheet 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 protective film-forming composite sheet 1C, the support sheet 10 is composed of only the base material 11. Then, the protective film forming film 13 is laminated on the first surface 11a of the base material 11 (the first surface 10a of the support sheet 10), and a part of the first surface 13a of the protective film forming film 13, that is, the peripheral portion. The jig adhesive layer 16 is laminated in a nearby region, and a region of the first surface 13a of the protective film forming film 13 where the jig adhesive layer 16 is not laminated and a jig adhesive layer. The release film 15 is laminated on the surface 16 a (upper surface and side surface) of 16.

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

  The protective film-forming composite sheet 1C shown in FIG. 4 is, like the protective film-forming composite sheet 1A shown in FIG. 2, in the state where the release film 15 is removed, on the first surface 13a of the protective film-forming film 13. The back surface of a semiconductor wafer (not shown) is attached, and further, the upper surface of the surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame for use.

FIG. 5: is sectional drawing which shows typically the composite sheet for protective film formation which concerns on other embodiment of this 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 base material 11, and the release film 15 is laminated on the entire first surface 13a of the protective film forming film 13. Has been done.

  In the protective film forming composite sheet 1D, the protective film forming film 13 has an image definition 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 in that the release film 15 is removed, and the first surface 13a of the protective film-forming film 13 is removed. Of these, the back surface of a semiconductor wafer (not shown) is attached to a part of the region on the center side, and the region in the vicinity of the peripheral edge is attached to a jig such as a ring frame for use.

FIG. 6 is a cross-sectional view schematically showing a protective film-forming composite sheet 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 the base material 11, the adhesive layer 12 on the base material 11, and the protective film forming film 23 on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, and in other words, the protective film forming composite sheet 1E has the protective film forming film 23 laminated on the first surface 10a of the supporting sheet 10. It has a different configuration. The protective film forming composite sheet 1E further includes a release film 15 on the protective film forming film 23.

  In the protective film-forming composite sheet 1E, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film is formed on a part of the first surface 12a of the pressure-sensitive adhesive layer 12, that is, the central region. Film 23 is laminated. Then, in the first surface 12a of the pressure-sensitive adhesive layer 12, the release film 15 is provided on a region where the protective film forming film 23 is not laminated and on the surface 23a (upper surface and side surface) of the protective film forming film 23. It is stacked.

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

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

  In the protective film forming composite sheet 1E shown in FIG. 6, the back surface of the semiconductor wafer (not shown) is attached to the front surface 23a of the protective film forming film 23 in a state where the release film 15 is removed. A region of the first surface 12 a of the 12 where the protective film forming film 23 is not laminated is attached to a jig such as a ring frame and used.

FIG. 7 is a cross-sectional view schematically showing a protective film-forming composite sheet according to still another embodiment of the present invention.
The protective film-forming composite sheet 1F shown here is treated on the first surface 12a of the pressure-sensitive adhesive layer 12 in a region where the protective film-forming film 23 is not laminated in the same manner as those shown in FIGS. 2 and 4. The protective sheet forming composite sheet 1E is the same as the protective film forming composite sheet 1E shown in FIG. 6 except that the component adhesive layer 16 is laminated. That is, the protective film-forming composite sheet 1F includes the base material 11, the adhesive layer 12 on the base material 11, the protective film forming film 23 on the adhesive layer 12, and the first adhesive layer 12 The jig adhesive layer 16 is laminated in a region of the one surface 12a where the protective film forming film 23 is not laminated. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, and in other words, the protective film forming composite sheet 1F has the protective film forming film 23 laminated on the first surface 10a of the supporting sheet 10. It has a different configuration. The protective film-forming composite sheet 1F further includes a release film 15 on the protective film forming film 23.

  In the protective film-forming composite sheet 1F, the pressure-sensitive adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film is formed on a part of the first surface 12a of the pressure-sensitive adhesive layer 12, that is, the central region. Film 23 is laminated. Then, in the first surface 12a of the pressure-sensitive adhesive layer 12, the release film 15 is provided on a region where the protective film forming film 23 is not laminated and on the surface 23a (upper surface and side surface) of the protective film forming film 23. It is stacked.

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

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

  In the protective film forming composite sheet 1F shown in FIG. 7, the back surface of the semiconductor wafer (not shown) is attached to the front surface 23a of the protective film forming film 23 in a state where the release film 15 is removed. The upper surface of the surface 16a of the adhesive layer 16 is used by being attached to a jig such as a ring frame.

  As described above, the protective film-forming composite sheet may have a jig adhesive layer regardless of the form of the support sheet and the protective film forming film. However, normally, as shown in FIGS. 2 and 4, a protective film-forming composite sheet having a jig adhesive layer has a jig adhesive layer on a protective film forming film. Is preferred.

  The composite sheet for forming a protective film according to one embodiment of the present invention is not limited to the one shown in FIGS. 2 to 7, and is a part of the one shown in FIGS. 2 to 7 as long as the effect of the present invention is not impaired. The configuration may be changed or deleted, or another configuration may be added to the configuration described so far.

For example, in the protective film-forming composite sheet shown in FIGS. 4 and 5, an intermediate layer may be provided between the base material 11 and the protective film-forming film 13. As the intermediate layer, any one can be selected according to the purpose.
Further, in the protective film-forming composite sheet shown in FIGS. 2, 3, 6 and 7, an intermediate layer may be provided between the base material 11 and the pressure-sensitive adhesive layer 12. That is, in the protective film-forming composite sheet of the present invention, the support sheet may be formed by laminating the base material, the intermediate layer, and the adhesive layer in this order in the thickness direction thereof. Here, the intermediate layer is the same as the intermediate layer which may be provided in the composite sheet for forming a protective film shown in FIGS. 4 and 5.
In addition, in the protective film-forming composite sheet shown in FIGS. 2 to 7, layers other than the intermediate layer may be provided at arbitrary positions.
Further, in the protective film-forming composite sheet, a gap may be partially formed between the release film and the layer in direct contact with the release film.
Further, 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 protective film-forming composite sheet of the present invention, a layer such as a pressure-sensitive adhesive layer which is in direct contact with the protective film-forming film in the supporting sheet may be non-energy ray curable or energy ray curable. May be sex.
When it is non-energy ray curable, the composite film for forming a protective film can be manufactured at a lower cost.
When the protective sheet-forming composite sheet is energy ray-curable, it becomes easier to adjust the adhesive force, and it becomes easier to adjust the suitability for dicing and pickup.

In the present invention, “non-curable” means a property that does not cure by heating or irradiation with energy rays, and “thermosetting” means a property that cures by heating, and “energy”. The term "curable by radiation" means the property of being cured by irradiation with energy rays.
In the present invention, the "energy ray" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, electron beams and the like.

  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 ray source. The electron beam can be generated by an electron beam accelerator or the like.

The support sheet may be transparent or opaque, and may be colored depending on the purpose.
When the protective film-forming film has energy ray curability, the support sheet preferably transmits energy rays.

For example, in the support sheet, the transmittance of light having a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, the degree of curing of the protective film forming film is further improved when the protective film forming film is irradiated with energy rays (ultraviolet rays) through the support sheet.
On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 375 nm is not particularly limited, but can be 95%, for example.

Further, in the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
When the light transmittance is in such a range, it is possible to read the laser-printed characters, symbols, patterns or the like printed on the semiconductor wafer or the semiconductor chip through the protective sheet through the protective film. Therefore, it is possible to inspect for the presence of foreign matter between the printing, the grinding marks on the back surface of the semiconductor wafer or the semiconductor chip, or the semiconductor wafer or the semiconductor chip and the protective film. If there is a foreign substance, the state of the foreign substance can be inspected.
On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 532 nm is not particularly limited, but may be 95%, for example.

Further, in the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, it is possible to read the laser-printed characters, symbols, patterns or the like printed on the semiconductor wafer or the semiconductor chip through the protective sheet through the protective film. Therefore, it is possible to inspect for the presence of foreign matter between the printing, the grinding marks on the back surface of the semiconductor wafer or the semiconductor chip, or the semiconductor wafer or the semiconductor chip and the protective film. If there is a foreign substance, the state of the foreign substance can 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 can be 95%, for example.
Next, each layer constituting the support sheet will be described in more detail.

-Substrate The substrate is in the form of a sheet or a film, and examples of the constituent material thereof 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); other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin. Polyolefins: ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-norbornene copolymers and other ethylene-based copolymers (ethylene as a monomer Polyvinyl chloride, vinyl chloride copolymer such as vinyl chloride copolymer (resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Naphtha Polyesters such as acrylate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalene dicarboxylate, wholly aromatic polyesters in which all constituent units have an aromatic cyclic group; Polymers; poly (meth) acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones; polyether ketones and the like.
Further, examples of the resin include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than that is preferably one in which the amount of the resin other than polyester is relatively small.
Further, as the resin, for example, a cross-linked resin obtained by crosslinking one or two or more of the resins exemplified above; a modification of an ionomer or the like using one or two or more of the resins exemplified above Resins are also included.

  In this specification, the term “(meth) acrylic acid” includes both “acrylic acid” and “methacrylic acid”. The same applies to terms similar to (meth) acrylic acid, and for example, "(meth) acryloyl group" is a concept including both "acryloyl group" and "methacryloyl group", and "(meth) acrylate" "" Is a concept including both "acrylate" and "methacrylate".

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

  The substrate may be composed of one layer (single layer) or may be composed 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. The combination of layers is not particularly limited.

The thickness of the base material 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 base material is in such a range, the flexibility of the composite sheet for forming a protective film and the stickability to a semiconductor wafer or a semiconductor chip are further improved.
Here, the "base material thickness" means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers means the total thickness of all layers constituting the base material. means.

  It is preferable that the base material has a high thickness accuracy, that is, a base material in which the thickness variation is suppressed regardless of the site. Of the above-mentioned constituent materials, examples of materials that can be used to form such a highly accurate base material include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like. Is mentioned.

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

The optical characteristics of the base material only need to satisfy the optical characteristics of the support sheet described above. That is, the base material may be transparent or opaque, and may be colored depending on the purpose, or another layer may be vapor-deposited.
When the protective film-forming film has energy ray curability, the base material is preferably one that transmits energy rays.

The substrate is roughened by sandblasting, solvent treatment, corona discharge treatment, electron beam irradiation treatment, plasma treatment in order to improve adhesion with other layers such as an adhesive layer provided thereon. The surface may be subjected to oxidation treatment such as ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, or the like.
Further, the base material may have a surface subjected to a primer treatment.
In addition, the base material prevents the base material from adhering to another sheet and the base material from adhering to the adsorption table when the antistatic coating layer and the composite sheet for forming a protective film are stacked and stored. It may have a layer or the like.
Among these, the base material is preferably one whose surface has been subjected to electron beam irradiation treatment, in order to suppress the generation of fragments of the base material due to the friction of the blade during dicing.

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

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

  In the present invention, "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness, and for example, not only the resin itself having adhesiveness, Also included are resins that exhibit adhesiveness when used in combination with other components such as additives, and resins that exhibit adhesiveness in the presence of a trigger such as heat or water.

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

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 pressure-sensitive adhesive layer" means the thickness of the whole pressure-sensitive adhesive layer, for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers is the total of all layers constituting the pressure-sensitive adhesive layer. Means the thickness of.

The optical properties of the pressure-sensitive adhesive layer may be such that they 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.
When the protective film-forming film has energy ray curability, the adhesive layer preferably transmits energy rays.

  The pressure-sensitive adhesive layer may be formed using an energy ray-curable pressure-sensitive adhesive or may be formed using a non-energy ray-curable pressure-sensitive adhesive. The physical properties of the pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can be easily adjusted 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, the pressure-sensitive adhesive layer can be formed at a desired site by applying the pressure-sensitive adhesive composition to the surface on which the pressure-sensitive adhesive layer is to be formed and drying it as necessary. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer. In the present specification, the “normal temperature” means a temperature at which it is not cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

  The 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. Examples include methods using various coaters such as a Meyer bar coater and a kiss coater.

  When the pressure-sensitive adhesive layer is provided on the base material, for example, the pressure-sensitive adhesive composition may be applied onto the base material and dried as necessary to laminate the pressure-sensitive adhesive layer on the base material. Further, when the pressure-sensitive adhesive layer is provided on the substrate, for example, by coating the pressure-sensitive adhesive composition on the release film, and drying it if necessary, to form the pressure-sensitive adhesive layer on the release film. Alternatively, the exposed surface of the pressure-sensitive adhesive layer may be attached to one surface of the base material to laminate the pressure-sensitive adhesive layer on the base material.

  When the pressure-sensitive adhesive layer is energy ray-curable, examples of the energy ray-curable pressure-sensitive adhesive composition include a non-energy ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter, referred to as “pressure-sensitive adhesive resin (I- 1a) ") and an energy ray-curable compound, and a side chain of the non-energy ray-curable adhesive resin (I-1a). A pressure-sensitive adhesive composition (I- containing an energy ray-curable pressure-sensitive adhesive resin (I-2a) (hereinafter, may be abbreviated as "pressure-sensitive adhesive resin (I-2a)") having an unsaturated group introduced therein. 2); and the pressure-sensitive adhesive composition (I-3) containing the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable compound.

  When the pressure-sensitive adhesive layer is non-energy ray curable, the non-energy ray curable pressure sensitive adhesive composition may be, for example, a pressure sensitive adhesive composition containing the non-energy ray curable pressure sensitive adhesive resin (I-1a). (I-4) and the like.

[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, these pressure-sensitive adhesive compositions are included. Then, the adhesive resin (I-1a) in the “adhesive composition (I-1) to (I-4)” is preferably an acrylic resin.

Examples of the acrylic resin include acrylic polymers having at least a structural unit derived from an alkyl (meth) acrylate ester.
Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferred.

The acrylic polymer preferably further has a constituent unit derived from a functional group-containing monomer, in addition to the constituent unit derived from an alkyl (meth) acrylate.
As the functional group-containing monomer, for example, the functional group serves as a starting point of crosslinking by reacting with a crosslinking agent described below, or the functional group reacts with an unsaturated group in an unsaturated group-containing compound described below. Examples of the acrylic polymer include those capable of introducing an unsaturated group into the side chain.

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

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

  In the pressure-sensitive adhesive compositions (I-1) to (I-4), the constitutional unit contained in the acrylic resin such as the acrylic polymer may be only one kind, or two or more kinds, or two or more kinds. If so, the combination and ratio thereof can be arbitrarily selected.

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

  The pressure-sensitive adhesive composition (I-1) or the pressure-sensitive adhesive composition (I-4) contains the adhesive resin (I-1a), which may be only one kind, two or more kinds, or two or more kinds. In that case, those combinations and ratios can be arbitrarily selected.

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

[Adhesive resin (I-2a)]
The adhesive resin (I-2a) in the adhesive compositions (I-2) and (I-3) has, for example, an energy ray-polymerizable unsaturated group due to a functional group in the adhesive resin (I-1a). It is obtained by reacting an unsaturated group-containing compound having a group.

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

  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 kind, or two or more kinds, and when two or more kinds are contained, The combination and the ratio can be arbitrarily selected.

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

[Energy ray curable compound]
Examples of the energy ray-curable compound in the pressure-sensitive adhesive compositions (I-1) and (I-3) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays. To be

Among the energy ray curable compounds, examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4 -Poly (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Examples thereof include (meth) acrylate.
Among the energy ray-curable compounds, examples of the oligomer include oligomers obtained by polymerizing the above-exemplified monomers.

  The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) or (I-3) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination thereof and The ratio can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the energy ray-curable compound with respect 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 0.01 to 400 parts by mass based on 100 parts by mass of the adhesive resin (I-2a). It is preferable.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from a (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), the pressure-sensitive adhesive composition ( It is preferable that I-1), (I-3) or (I-4) further contains a crosslinking agent.
In addition, when the acrylic polymer having a constitutional unit derived from a functional group-containing monomer, similar to that in the adhesive resin (I-1a), is used as the adhesive resin (I-2a), for example, the adhesive composition The product (I-2) may further contain a crosslinking agent.

The cross-linking agent in the adhesive resins (I-1a) and (I-2a) reacts with the functional group to cause adhesive resins (I-1a) or adhesive resins (I-2a) to react with each other. Cross-link.
Examples of the cross-linking agent include isocyanate-based cross-linking agents (cross-linking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy-based cross-linking agents such as ethylene glycol glycidyl ether ( Crosslinking agent having glycidyl group); aziridine-based crosslinking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (crosslinking agent having aziridinyl group); A cross-linking agent having a chelate structure); an isocyanurate-based cross-linking agent (cross-linking agent having an isocyanuric acid skeleton), and the like.

  The cross-linking agents contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof are arbitrarily set. You can choose.

In the pressure-sensitive adhesive composition (I-1), (I-3) or (I-4), the content of the cross-linking agent is 0 with respect to 100 parts by mass of the content of the adhesive resin (I-1a). It is preferably 0.01 to 50 parts by mass.
In the pressure-sensitive adhesive composition (I-2), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the adhesive resin (I-2a).

[Photopolymerization initiator]
Pressure-sensitive adhesive composition (I-1), (I-2) and (I-3) (hereinafter, including these pressure-sensitive adhesive compositions, "pressure-sensitive adhesive compositions (I-1) to (I-3)" “Abbreviated as”) may further contain a photopolymerization initiator. The curing reaction of the pressure-sensitive adhesive compositions (I-1) to (I-3) containing the photopolymerization initiator sufficiently proceeds even when irradiated with a relatively low energy ray such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, and other benzoin compounds; acetophenone, 2-hydroxy. Acetophenone compounds such as 2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine Acylphosphine oxide compounds such as oxides and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Sulfidation of benzylphenyl sulfide, tetramethylthiuram monosulfide, etc. Compounds; α-ketol compounds such as 1-hydroxycyclohexyl phenyl 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-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 1-chloroanthraquinone, 2-chloroanthraquinone, etc. Quinone compounds of.
Further, as the photopolymerization initiator, for example, a photosensitizer such as amine can be used.

  The photopolymerization initiators contained in the pressure-sensitive adhesive compositions (I-1) to (I-3) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio are It can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the energy ray-curable compound.
In the pressure-sensitive 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 pressure-sensitive adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 to 100 parts by mass with respect to the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray-curable compound. It is preferably 20 parts by mass.

[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 components, as long as the effects of the present invention are not impaired.
Examples of the other additives include antistatic agents, antioxidants, softening agents (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers. Known additives such as a reaction retarder, a crosslinking accelerator (catalyst) and the like can be mentioned.
The reaction retarder means, for example, the pressure-sensitive adhesive compositions (I-1) to ((-1) during storage by the action of the catalyst mixed in the pressure-sensitive adhesive compositions (I-1) to (I-4). In I-4), it is intended to suppress the progress of an unintended crosslinking reaction. Examples of the reaction retarder include those which form a chelate complex by chelating with respect to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule. Can be mentioned.

  The other additives contained in the pressure-sensitive adhesive compositions (I-1) to (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio are It 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 depending on the type.

[solvent]
The pressure-sensitive adhesive composition (I-1) to (I-4) may contain a solvent. Since the pressure-sensitive adhesive compositions (I-1) to (I-4) contain the solvent, the suitability for coating on the surface to be coated is improved.

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

  The solvent contained in the pressure-sensitive adhesive composition (I-1) to (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, their combination and ratio are arbitrarily selected. it can.

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

-Production method of pressure-sensitive adhesive composition The pressure-sensitive adhesive composition such as pressure-sensitive adhesive compositions (I-1) to (I-4) has the pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive. It is obtained by blending each component for constituting the agent composition.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
The method of mixing the respective components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; a method of adding ultrasonic waves to mix It may be selected appropriately.
The temperature and time at the time of adding and mixing 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 thermosetting protective film A preferable film for forming a thermosetting protective film is, for example, a film containing a polymer component (A) and a thermosetting component (B). The polymer component (A) is a component that can be regarded as formed by a polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component that can undergo a curing reaction by using heat as a reaction trigger. In the present invention, the polymerization reaction also includes a polycondensation reaction.

  The thermosetting protective film-forming film may be composed of one layer (single layer) or may be composed of two or more layers. When the thermosetting protective film forming film comprises a plurality of layers, these plurality of layers may be the same or different from each other. Here, "the plural layers may be the same or different from each other" means the same as in the case of the above-mentioned base material. When the plurality of layers are different from each other, the combination of the 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 not less than the lower limit value, a protective film having a higher protective ability can be formed when the thermosetting protective film-forming film is used as the protective film. Further, when the thickness of the thermosetting protective film forming film is not more than the upper limit value, it is possible to prevent the film from having an excessive thickness.
Here, the "thickness of the thermosetting protective film forming film" means the total thickness of the thermosetting protective film forming film, for example, the thermosetting protective film forming film consisting of a plurality of layers. The thickness means the total thickness of all layers constituting the thermosetting protective film forming film.

The thermosetting protective film-forming film is attached to the back surface of the semiconductor wafer and the curing conditions for curing are not particularly limited as long as the protective film has a degree of curing sufficient to exhibit its function. It may be appropriately selected depending on the type of the protective film forming film.
For example, the heating temperature during curing of the thermosetting protective film-forming film is preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 110 ° C. or higher and 180 ° C. or lower, and 120 ° C. or higher and 170 ° C. or lower. It is particularly preferable that The heating time during 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. preferable.

<< Thermosetting protective film forming composition >>
The thermosetting protective film-forming film can be formed using the thermosetting protective film-forming composition containing the constituent material. For example, by applying the composition for forming a thermosetting protective film to the surface to be formed of the film for forming a thermosetting protective film, and drying it if necessary, to form a thermosetting protective film on the target site. A film can be formed. The content ratio of the components that do not vaporize at room temperature in the thermosetting protective film-forming composition is usually the same as the content ratio of the components of the thermosetting protective film-forming film. Here, "normal temperature" is as described above.

  The thermosetting protective film-forming composition can be applied, for example, by the same method as in the case of applying the pressure-sensitive adhesive composition described above.

  The drying conditions of the thermosetting protective film-forming composition are not particularly limited, but the thermosetting protective film-forming composition, when containing a solvent described below, is preferably dried by heating, in this case, For example, it is preferable to dry at 70 ° C. or higher and 130 ° C. or lower for 10 seconds or longer and 5 minutes or shorter.

<Thermosetting protective film forming composition (III-1)>
Examples of the thermosetting protective film-forming composition include a thermosetting protective film-forming composition (III-1) containing a polymer component (A) and a thermosetting component (B) (in the present specification). May be abbreviated as "composition (III-1)") and the like.

[Polymer component (A)]
The polymer component (A) is a polymer compound for imparting film forming properties and flexibility to the thermosetting protective film forming film.
The polymer component (A) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination thereof. And the ratio 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 (having siloxane bond) Resin), rubber resin (resin having a rubber structure), phenoxy resin, thermosetting polyimide and the like, and acrylic resin is preferable.

Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 or more and 2,000,000 or less, and more preferably 100,000 or more and 15,000,000 or less. When the weight average molecular weight of the acrylic resin is not less than the lower limit, the handling property and shape stability (temporal stability during storage) of the thermosetting protective film-forming film are improved. Further, when the weight average molecular weight of the acrylic resin is not more than the upper limit value, the thermosetting protective film-forming film easily follows the uneven surface of the adherend, and the adherend and the thermosetting protective film are formed. Generation of voids and the like between the film and the film for use is further 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 higher and 70 ° C. or lower, and more preferably −30 ° C. or higher and 50 ° C. or lower. When the Tg of the acrylic resin is at least the above lower limit, the adhesive force between the protective film and the support sheet (adhesive layer) is suppressed, and the peelability of the support sheet is improved. Further, when the Tg of the acrylic resin is not more than the upper limit value, the adhesion of the protective film to the adherend is improved.

  The acrylic resin is selected from, for example, one or more polymers of (meth) acrylic acid ester; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N-methylolacrylamide. Examples thereof include copolymers of two or more kinds of monomers.

Examples of the (meth) acrylic acid ester that constitutes the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate. ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic Heptyl acid, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate Undecyl (meth) acrylate, dodecyl (meth) acrylate ((meth) acrylic acid Uryl), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl acrylate), (meth) An alkyl group that constitutes an alkyl ester, such as heptadecyl acrylate and octadecyl (meth) acrylate (stearyl (meth) acrylate), is a (meth) acrylic acid alkyl ester having a chain structure having 1 to 18 carbon atoms;
(Meth) acrylic acid cycloalkyl esters such as isobornyl (meth) acrylic acid and dicyclopentanyl (meth) acrylic acid;
Aralkyl esters of (meth) acrylic acid such as benzyl (meth) acrylate;
(Meth) acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl ester;
(Meth) acrylic acid imide;
Glycidyl group-containing (meth) acrylic acid ester 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 ) Hydroxy group-containing (meth) acrylates such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic acid esters such as N-methylaminoethyl (meth) acrylic acid. Here, the "substituted amino group" means a group formed 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, one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc., in addition to the (meth) acrylic acid ester. May be obtained by copolymerization.

  The monomer that constitutes the acrylic resin may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

  The acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group and an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) described below, or may be directly bonded to another compound without the crosslinking agent (F). . When the acrylic resin is bonded to another compound through the functional group, the reliability of the package obtained by using the composite film 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 sometimes simply abbreviated as “thermoplastic resin”) is used alone without using an acrylic resin. Or may be used in combination with an acrylic resin. By using the thermoplastic resin, the peelability of the protective film from the support sheet is improved, or the thermosetting protective film forming film easily follows the uneven surface of the adherend, and the adherend and the thermosetting Occurrence of voids and the like between the film and the film for forming a protective film may be further suppressed.

  The weight average molecular weight of the thermoplastic resin is preferably 1,000 or more and 100,000 or less, more preferably 3,000 or more and 80,000 or less. Here, the “weight average molecular weight” is as described above.

  The glass transition temperature (Tg) of the thermoplastic resin is preferably −30 to 150 ° C., more preferably −20 to 120 ° C.

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

  The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof. Can 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, of the polymer component (A) of the thermosetting protective film-forming film). The content) 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, regardless of the type of the polymer component (A).

  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 , Polymer component (A) and thermosetting component (B).

[Thermosetting component (B)]
The thermosetting component (B) is a component for curing the thermosetting protective film-forming film to form a hard protective film.
The thermosetting component (B) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, or two or more kinds, and when two or more kinds are contained, The combination and the ratio can be arbitrarily selected.

  Examples of the thermosetting component (B) include epoxy thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, silicone resin and the like, and epoxy thermosetting resin is preferable.

(Epoxy thermosetting resin)
The epoxy thermosetting resin comprises an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination thereof. And the ratio can be arbitrarily selected.

・ Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones, for example, polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and hydrogenated product thereof, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, Bifunctional or higher functional epoxy compounds such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and phenylene skeleton type epoxy resin can be mentioned.

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

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy groups of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction with (meth) acrylic acid or a derivative thereof.
Further, 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 an aromatic ring or the like which constitutes 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). Examples thereof include an acrylamide group, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but from the viewpoint of the curability of the thermosetting protective film-forming film and the strength and heat resistance of the protective film after curing, it is 300 or more and 30,000 or less. Is more preferable, 300 or more and 10000 or less is more preferable, 300 or more and 3000 or less is particularly preferable.
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 the epoxy resin (B1), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.

・ Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is dehydrated, and the like, and the phenolic hydroxyl group, an amino group, or an acid group is dehydrated. It is preferably a group, and more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of the phenol-based 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. .
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.
As the thermosetting agent (B2) having an unsaturated hydrocarbon group, for example, a compound obtained by substituting a part of a hydroxyl group of a phenol resin with a group having an unsaturated hydrocarbon group, an aromatic ring of a phenol resin, Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.

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

In the thermosetting agent (B2), for example, the resin component such as a polyfunctional phenol resin, a novolac type phenol resin, a dicyclopentadiene type phenol resin, or an aralkyl type phenol resin has a number average molecular weight of 300 or more and 30,000 or less. It is more preferably 400 or more and 10,000 or less, and particularly preferably 500 or more and 3000 or less.
The molecular weight of the non-resin component such as biphenol or dicyandiamide in the thermosetting agent (B2) is not particularly limited, but is preferably 60 or more and 500 or less, for example.

  As the thermosetting agent (B2), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, their combination and ratio can be arbitrarily selected.

  In the composition (III-1) and the thermosetting protective film forming film, the content of the thermosetting agent (B2) is 0.1 parts by mass or more based on 100 parts by mass of the epoxy resin (B1). It is preferably 500 parts by mass or less, and more preferably 1 part by mass or more and 200 parts by mass or less. When the content of the thermosetting agent (B2) is equal to or more than the lower limit value, the thermosetting protective film-forming film is more easily cured. Further, when the content of the thermosetting agent (B2) is not more than the upper limit value, the moisture absorption rate of the thermosetting protective film-forming film is reduced, and the composite sheet for forming a protective film was obtained. Improves package reliability.

  In the composition (III-1) and the thermosetting protective film forming 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 content of the polymer component (A) 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 40 parts by mass or more and 150 parts by mass with respect to 100 parts by mass. It is particularly preferable that the amount is less than or equal to parts by mass. When the content of the thermosetting component (B) is in such a range, the adhesive force between the protective film and the support sheet is suppressed, and the releasability of the support sheet is improved.

[Curing accelerator (C)]
The composition (III-1) and the thermosetting protective film-forming 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, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like imidazoles (one or more hydrogen atoms other than hydrogen atoms Imidazole substituted with a group); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylphosphonium tetraphenylborate Tetraphenyl boron salts such as triphenyl phosphine tetraphenyl borate and the like.

  The curing accelerator (C) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination thereof. And the ratio can be arbitrarily selected.

  When the curing accelerator (C) is used, the content of the curing accelerator (C) in the composition (III-1) and the thermosetting protective film-forming film is 100% by weight of the thermosetting component (B). It is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 7 parts by mass or less with respect to parts by mass. When the content of the curing accelerator (C) is equal to or more than the lower limit value, the effect of using the curing accelerator (C) can be more remarkably obtained. Further, when the content of the curing accelerator (C) is not more than the upper limit value, for example, the highly polar curing accelerator (C) is contained in the thermosetting protective film forming film under high temperature and high humidity conditions. In the above, the effect of suppressing segregation by moving to the adhesion interface side with the adherend is enhanced, and the reliability of the semiconductor chip with a protective film obtained by using the composite sheet for forming a protective film is further improved.

[Filler (D)]
The composition (III-1) and the thermosetting protective film-forming film may contain a filler (D). Since the thermosetting protective film-forming film contains the filler (D), the protective film obtained by curing the thermosetting protective film-forming film can easily adjust the thermal expansion coefficient. By optimizing the expansion coefficient with respect to the object for forming the protective film, the reliability of the semiconductor chip with the protective film obtained by using the composite sheet for forming the protective film is further improved. In addition, when the thermosetting protective film forming film contains the filler (D), it is possible to reduce the moisture absorption rate of the protective film and improve the heat dissipation.

The filler (D) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferable inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc .; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Products; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.

The average particle diameter of the filler (D) is preferably 10 μm or less. By setting the average particle size to 10 μm or less, it becomes easy to adjust the image clarity of the protective film-forming film and the protective film to 110 or more. In order to further improve the 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 size is small, the image clarity tends to decrease due to the diffusion of light.

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

  When the filler (D) is used, 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 thermosetting protective film forming film). Content of the filler (D)) 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 15 parts by mass or more and 60 parts by mass or less. It is particularly preferable that When the content of the filler (D) is in such a range, it becomes easier to adjust the above-mentioned thermal expansion coefficient, so that it is possible to manufacture a highly reliable chip, and it is possible to obtain an image sharpness within a range. It becomes possible to do. Further, when the filler (D) is contained in an amount of more than 80% by mass, the image clarity tends to be lowered although it depends on the particle diameter of the filler (D).

[Coupling agent (E)]
The composition (III-1) and the thermosetting protective film-forming 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, it is possible to improve the adhesiveness and adhesiveness of the thermosetting protective film-forming film to an adherend. it can. Further, by using the coupling agent (E), the film obtained by curing the thermosetting protective film forming 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 the functional group of the polymer component (A), thermosetting component (B), etc., and is preferably a silane coupling agent. More preferable.
Examples of the preferable silane coupling agent include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyne Examples include trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. To be

  The coupling agent (E) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination thereof. And the ratio can be arbitrarily selected.

  When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the thermosetting protective film-forming film is the polymer component (A) and the thermosetting component. The total content of (B) 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 0.1 It is particularly preferable that the amount is 5 parts by mass or more and 5 parts by mass or less. When the content of the coupling agent (E) is at least the lower limit value, the dispersibility of the filler (D) in the resin is improved, and the thermosetting protective film-forming film is adhered to an adherend. The effect of using the coupling agent (E), such as improvement in properties, can be more remarkably obtained. Further, when the content of the coupling agent (E) is equal to or less than the upper limit value, the generation of outgas is further suppressed.

[Crosslinking agent (F)]
As the polymer component (A), those having a functional group such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxy group or an isocyanate group, which can be bonded to other compounds, such as the above-mentioned acrylic resin. When used, the composition (III-1) and the thermosetting protective film-forming film may contain a cross-linking agent (F) for bonding the functional group to another compound for cross-linking. By crosslinking with the crosslinking agent (F), the initial adhesive force and cohesive force of the thermosetting protective film-forming film can be adjusted.

  As the cross-linking agent (F), for example, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group), etc. Is mentioned.

  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 are collectively referred to as "aromatic polyvalent isocyanate compound etc." Abbreviated); trimers such as the aromatic polyvalent isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compounds and the like with polyol compounds Etc. The "adduct" is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound or an alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil or the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include a xylylene diisocyanate adduct of trimethylolpropane as described below. Further, the “terminal isocyanate urethane prepolymer” is as described above.

  More specific examples of the organic polyvalent isocyanate compound include 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; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate for all or part of the hydroxyl groups of propane and other polyols Like lysine diisocyanate and the like; the compound or two or more are added.

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

  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 cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, a reaction between the cross-linking agent (F) and the polymer component (A) gives a thermosetting protective film-forming film. A crosslinked structure can be easily introduced.

  The cross-linking agent (F) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination thereof and The ratio can be arbitrarily selected.

  When the cross-linking agent (F) is used, the content of the cross-linking agent (F) in the composition (III-1) is 0.01 parts by mass or more based on 100 parts by mass of the content of the polymer component (A). It is preferably 20 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 5 parts by mass or less. When the content of the cross-linking agent (F) is at least the lower limit value, the effect of using the cross-linking agent (F) can be more remarkably obtained. Further, when the content of the crosslinking agent (F) is not more than the upper limit value, excessive use of the crosslinking agent (F) is suppressed.

[Energy ray curable resin (G)]
The composition (III-1) may contain the energy ray-curable resin (G). Since the thermosetting protective film-forming film contains the energy ray-curable resin (G), its characteristics can be changed by irradiation with energy rays.

The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound.
Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.

  Examples of the acrylate 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-hexanediol di (meth) acrylate and the like (meth) acrylate containing a chain aliphatic skeleton; Cycloaliphatic skeleton-containing (meth) acrylate such as cyclopentanyl di (meth) acrylate; Polyalkylene glycol (meth) acrylate such as polyethylene glycol di (meth) acrylate; Rigoesuteru (meth) acrylate; urethane (meth) acrylate oligomer, epoxy-modified (meth) acrylate; the polyalkylene glycol (meth) Polyether (meth) acrylates other than the acrylates; itaconic acid oligomer, and the like.

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

  The energy ray-curable compound used for the polymerization may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

  The energy ray-curable resin (G) contained in the composition (III-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may 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, and more preferably 5% by mass or more and 90% by mass or less. It is particularly preferable that the content is 10% by mass or more and 85% by mass or less.

[Photopolymerization initiator (H)]
When the composition (III-1) contains the energy ray-curable resin (G), it contains a photopolymerization initiator (H) in order to efficiently advance the polymerization reaction of the energy ray-curable resin (G). May be.

Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal. Benzoin compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one and other acetophenone compounds; bis (2,2 Acylphosphine oxide compounds such as 4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzylphenyl sulfide and tetramethylthiuram Sulfide compounds such as nosulfides; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diacetyl etc. Diketone compound; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone, etc. Is mentioned.
Examples of the photopolymerization initiator also include quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines.

  The photopolymerization initiator (H) contained in the composition (III-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.

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

[Colorant (I)]
The composition (III-1) and the thermosetting protective film-forming film may contain a colorant (I) as long as the effects of the invention are not impaired.
Examples of the colorant (I) include known pigments such as inorganic pigments, organic pigments and organic dyes.

  Examples of the organic pigments and organic dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, phthalocyanines. Dye, naphthalocyanine dye, naphtholactam dye, azo dye, condensed azo dye, indigo dye, perinone dye, perylene dye, dioxazine dye, quinacridone dye, isoindolinone dye, quinophthalone dye , Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol dyes, azomethine dyes, benzimidazo Ron Dyes, pyranthrone pigments and threne 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 ( Examples thereof include indium tin oxide) dyes and ATO (antimony tin oxide) dyes.

  The colorant (I) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination thereof and The ratio can be arbitrarily selected.

  When the colorant (I) is used, the content of the colorant (I) in the thermosetting protective film-forming film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film and adjusting the light transmittance of the protective film, the print visibility in the case of performing laser printing on the wafer is improved. Can be adjusted. In addition, by adjusting the content of the colorant (I) in the thermosetting protective film forming film, it is possible to improve the design of the protective film and make it difficult to see the grinding marks on the back surface of the semiconductor wafer. Considering this point, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all components other than the solvent (that is, coloring of the thermosetting protective film-forming film). The content of the agent (I)) 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 0.1% by mass. It is particularly preferable that the content is 5 mass% or less. When the content of the colorant (I) is not less than the lower limit value, the effect of using the colorant (I) can be more remarkably obtained. Further, when the content of the colorant (I) is equal to or less than the upper limit value, an excessive decrease in light transmittance of the thermosetting protective film-forming film is suppressed.

[General-purpose additive (J)]
The composition (III-1) and the thermosetting protective film-forming film may contain a general-purpose additive (J) as long as the effects of the present invention are not impaired.
The general-purpose additive (J) may be a known one and can be arbitrarily selected according to the purpose and is not particularly limited, but preferable examples include, for example, a plasticizer, an antistatic agent, an antioxidant, a gettering agent and the like. Is mentioned.

The general-purpose additive (J) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one kind, or may be two or more kinds and, in the case of two or more kinds, a combination thereof. And the ratio can be arbitrarily selected.
The content of the general-purpose additive (J) in the composition (III-1) and the thermosetting protective film-forming film is not particularly limited and may be appropriately selected depending on the purpose.

[solvent]
The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. Examples include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
The solvent contained in the composition (III-1) may be only one type, or may be two or more types, and in the case of two or more types, their combination and ratio 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 mixed more uniformly.

<< Method for producing thermosetting protective film-forming composition >>
The thermosetting protective film-forming composition such as the composition (III-1) can be obtained by blending the respective components for constituting it.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by diluting any compounding component other than the solvent in advance. Alternatively, the solvent may be used by mixing with these compounding ingredients.
The method of mixing the respective components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; a method of adding ultrasonic waves to mix It may be selected appropriately.
The temperature and 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 higher and 30 ° C. or lower.

Film for forming an energy ray-curable protective film The film for forming an energy ray-curable protective film contains the energy ray-curable component (a).
In the energy ray-curable protective film-forming film, the energy ray-curable component (a) is preferably uncured, preferably has tackiness, more preferably uncured and tacky. Here, "energy ray" and "energy ray curability" are as described above.

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

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 not less than the lower limit value, a protective film having a higher protective ability can be formed when the energy ray-curable protective film forming film is used as the protective film. Further, when the thickness of the energy ray-curable protective film forming film is not more than the upper limit value, it is possible to prevent the film from having an excessive thickness.
Here, the "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 formation of an energy ray-curable protective film composed of a plurality of layers. The thickness of the film for use means the total thickness of all layers constituting the film for forming an energy ray-curable protective film.

The energy ray-curable protective film-forming film is attached to the back surface of the semiconductor wafer and cured to form a protective film, as long as the curing conditions are such that the protective film sufficiently exhibits its function. It is not particularly limited and may be appropriately selected depending on the type of the energy ray-curable protective film forming film.
For example, at the time of curing of the energy ray-curable protective film forming film, the illuminance of the energy ray is preferably 120 mW / cm ² or more 280 mW / cm ² or less. The light amount of the energy ray at the time of curing is preferably 200 mJ / cm ² or more and 1000 mJ / cm ² or less.

<< Energy ray curable protective film forming composition >>
The energy ray-curable protective film-forming film can be formed by using the energy ray-curable protective film-forming composition containing the constituent material. For example, the composition for forming an energy ray-curable protective film is applied to the surface on which the film for forming an energy ray-curable protective film is formed, and dried as necessary to protect the target area with the energy ray-curable film. A film forming film can be formed. In the composition for forming an energy ray-curable protective film, the ratio of the content of components that do not vaporize at room temperature is usually the same as the ratio of the content of the components of the film for forming an energy ray-curable protective film. . Here, "normal temperature" is as described above.

  The energy ray-curable protective film-forming composition can be applied, for example, by the same method as in the case of applying the pressure-sensitive adhesive composition described above.

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

<Energy ray curable protective film forming composition (IV-1)>
As the composition for forming an energy ray-curable protective film, for example, the composition for forming an energy ray-curable protective film (IV-1) containing the energy ray-curable component (a) (in the present specification, simply "May be abbreviated as" composition (IV-1) ") 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, imparts film-forming properties, flexibility, etc. to the energy-ray-curable protective film forming film, and protects the hard after curing. It is also a component for forming a film.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000, and an energy ray-curable group having a molecular weight of 100 to 80,000. The following compound (a2) may be mentioned.
At least a part of the polymer (a1) may be 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 80,000 or more and 2,000,000 or less)
Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 or more and 2,000,000 or less include, for example, an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, An acrylic resin (a1-1) formed by reacting an energy ray-curable compound (a12) having a group that reacts with the functional group and an energy ray-curable group such as an energy ray-curable double bond. To be

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

.Acrylic polymer having functional group (a11)
Examples of the functional group-containing acrylic polymer (a11) include those obtained by copolymerizing the functional group-containing acrylic monomer and the functional group-free acrylic monomer. In addition to the monomer, a monomer (non-acrylic monomer) other than the acrylic monomer may be copolymerized.
The acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method can be adopted as a polymerization method.

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

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

  Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid (monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, itaconic acid, maleic acid, citracone. Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above-mentioned ethylenically unsaturated dicarboxylic acids; and (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate. To be

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

  The acrylic monomer having the functional group, which constitutes the acrylic polymer (a11), may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily set. You can choose.

  Examples of the acrylic monomer having no functional group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic. Acid n-butyl, (meth) acrylate isobutyl, (meth) acrylate sec-butyl, (meth) acrylate tert-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl , 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, ( Undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl acrylate), (meth) acrylic acid Examples thereof include heptadecyl and octadecyl (meth) acrylate (stearyl (meth) acrylate), and the like, in which the alkyl group forming the alkyl ester has a chain structure having 1 to 18 carbon atoms, and the like (meth) acrylic acid alkyl ester. To be

  Examples of the acrylic monomer having no functional group include alkoxy such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Alkyl group-containing (meth) acrylic acid ester; (meth) acrylic acid ester having an aromatic group, including (meth) acrylic acid aryl ester such as phenyl (meth) acrylic acid; non-crosslinkable (meth) acrylamide and Derivatives thereof; (meth) acrylic acid esters having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like are also included. .

  The acrylic monomer having no functional group, which constitutes the acrylic polymer (a11), may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof are arbitrary. You can choose to.

Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene.
The non-acrylic monomer constituting the acrylic polymer (a11) may be only one kind, or two or more kinds, and in the case of two or more kinds, their combination and ratio can be arbitrarily selected.

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

  The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof are arbitrary. You can choose.

  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 acrylic resin (a1 of the energy ray-curable protective film forming film)). The content of (-1)) 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 10% by mass or more and 50% by mass or less. Particularly preferred.

・ Energy ray curable compound (a12)
The energy ray-curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having at least one species are preferable, and those having an isocyanate group as the group are more preferable. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

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

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

  The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or may be two or more types, and in the case of two or more types, their combination and ratio are arbitrary. You can choose to.

  In the acrylic resin (a1-1), the content of the energy ray-curable group derived from the energy ray-curable compound (a12) with respect to the content of the functional group derived from the acrylic polymer (a11). Is preferably 20 mol% or more and 120 mol% or less, more preferably 35 mol% or more and 100 mol% or less, and particularly preferably 50 mol% or more and 100 mol% or less. When the ratio of the content is within such a range, the adhesive force of the protective film after curing becomes larger. When the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the content ratio is 100 mol%. When the energy ray-curable compound (a12) is a polyfunctional compound (having two or more 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 100,000 or more and 2,000,000 or less, and more preferably 300,000 or more and 1500000 or less.
Here, the “weight average molecular weight” is as described above.

  When at least a part of the polymer (a1) is crosslinked with a crosslinking agent, the polymer (a1) is described as constituting the acrylic polymer (a11). A monomer that does not correspond to any of the monomers and has a group that reacts with a cross-linking agent may be polymerized and cross-linked at a group that reacts with the cross-linking agent, or the energy ray-curable compound ( The group derived from a12) that reacts with the functional group may be crosslinked.

  The polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be only one kind, or two or more kinds, and in the case of two or more kinds, The combination and the ratio can be arbitrarily selected.

(Compound (a2) having an energy ray-curable group and a molecular weight of 100 or more and 80,000 or less)
Examples of the energy ray-curable group having an energy ray-curable group and having a molecular weight of 100 or more and 80,000 or less (a2) include groups having an energy ray-curable double bond, and preferable examples include (meta ) Examples thereof include an acryloyl group and a vinyl group.

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

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

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

  The compound (a2) preferably has a weight average molecular weight of 100 or more and 30,000 or less, and more preferably 300 or more and 10,000 or less. Here, the “weight average molecular weight” is as described above.

  The compound (a2) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be only one kind, or may be two or more kinds and, in the case of two or more kinds, a combination thereof. And the ratio can be arbitrarily selected.

[Polymer (b) having no energy ray-curable group]
When the composition (IV-1) and the energy ray-curable protective film-forming film contain the compound (a2) as the energy ray-curable component (a), the polymer further has no energy ray-curable group. It is preferable to also contain (b).
At least a part of the polymer (b) may be 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, may be abbreviated as “acrylic polymer (b-1)”).

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

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

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-methacrylate. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Undecyl acid, dodecyl (meth) acrylate (lauryl (meth) acrylate), (meth ) Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl acrylate), heptadecyl (meth) acrylate, ( Examples thereof include (meth) acrylic acid alkyl ester such as octadecyl (meth) acrylic acid (stearyl (meth) acrylic acid) in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms.

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

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

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

As the polymer (b) having no energy ray-curable group, at least a part of which is crosslinked with a crosslinking agent, for example, one in which a reactive functional group in the polymer (b) is reacted with a crosslinking agent. Can be mentioned.
The reactive functional group may be appropriately selected according to the type of the cross-linking agent and is not particularly limited. For example, when the cross-linking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group and an amino group, and among these, a hydroxyl group having a high reactivity with an isocyanate group is preferable. When the cross-linking agent is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, and among these, a carboxy group having high reactivity with an epoxy group is preferable. . However, the reactive functional group is preferably a group other than a carboxy group from the viewpoint of preventing the corrosion of the circuit of the semiconductor wafer or the semiconductor chip.

  Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group. In the case of the acrylic polymer (b-1), any one or both of the acrylic monomer and the non-acrylic monomer, which are mentioned as the monomer constituting the acrylic polymer (b-1), have the reactive functional group. You can use it. For example, examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester. Examples of the acrylic monomer or non-acrylic monomer include those obtained by polymerizing a monomer in which one or two or more hydrogen atoms are substituted with the reactive functional group.

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

  The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10,000 or more and 2,000,000 or less from the viewpoint that the film-forming property of the composition (IV-1) becomes better. More preferably, 100,000 or more and 15,000,000 or less. Here, the “weight average molecular weight” is as described above.

  The polymer (b) containing no energy ray-curable group contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be only one kind, or may be two or more kinds. When there are more than one species, their combination and ratio can be arbitrarily selected.

  Examples of the composition (IV-1) include those containing one or both of the polymer (a1) and the compound (a2). And when the composition (IV-1) contains the compound (a2), it is preferable that the composition (IV-1) further contains a polymer (b) having no energy ray-curable group. In this case, the composition (IV) further contains (a1). It is also preferable to contain. Moreover, the composition (IV-1) may contain neither the compound (a2) but the polymer (a1) and the polymer (b) having no energy ray-curable group. .

  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 content of the compound (a2) is 10 parts by mass or more and 400 parts by mass or less based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. It is preferable that the amount is 30 parts by mass or more and 350 parts by mass or less.

  In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (that is, The total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the energy ray-curable protective film-forming film) is 5% by mass or more and 90% by mass or less. It is preferable that the amount is 10% by mass or more and 80% by mass or less, and particularly preferably 20% by mass or more and 70% by mass or less. When the ratio of the content of the energy ray-curable component is in such a range, the energy ray-curable film of the energy ray-curable protective film forming film has better energy ray curability.

  The composition (IV-1) is a thermosetting component, a filler, a coupling agent, a cross-linking agent, a photopolymerization initiator, a colorant, and a general-purpose additive other than the energy ray-curable component, depending on the purpose. You may contain 1 type (s) or 2 or more types selected from the group which consists of. 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 has an adhesive force to an adherend by heating. And the strength of the protective film formed from this energy ray-curable protective film-forming film is also improved.

  As the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant, and the general-purpose additive in the composition (IV-1), the heat in the composition (III-1) is used. The same as the curable component (B), filler (D), coupling agent (E), cross-linking agent (F), photopolymerization initiator (H), colorant (I) and general-purpose additive (J) Can be mentioned.

In the composition (IV-1), each of the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant, and the general-purpose additive may be used alone. However, two or more kinds may be used in combination, and when two or more kinds are used in combination, their combination and ratio can be arbitrarily selected.
The content of the thermosetting component, the filler, the coupling agent, the cross-linking agent, the photopolymerization initiator, the colorant, and the general-purpose additive in the composition (IV-1) may be appropriately adjusted according to the purpose. It is not particularly limited.

It is preferable that the composition (IV-1) further contains a solvent because the handling property thereof is improved by dilution.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
The solvent contained in the composition (IV-1) may be only one type, or may be two or more types.

<< Method for producing composition for forming energy ray-curable protective film >>
The energy ray-curable protective film forming composition such as the composition (IV-1) can be obtained by blending the respective components for constituting the same.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by diluting any compounding component other than the solvent in advance. Alternatively, the solvent may be used by mixing with these compounding ingredients.
The method of mixing the respective components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; a method of adding ultrasonic waves to mix It may be selected appropriately.
The temperature and 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 higher and 30 ° C. or lower.

-Non-curable protective film forming film A preferable non-curable protective film forming film contains, for example, a non-curable component (c). In the non-curable protective film-forming film, the non-curable component (c) may have no curability, may have adhesiveness to a support sheet, and may have an appropriate hardness for protecting a semiconductor wafer or a chip. preferable. Here, "non-curable" is as described above.

  The non-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 when it is a plurality of layers, these plurality of layers may be the same or different from each other. The combination of a plurality of layers is not particularly limited.

The thickness of the non-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 non-curable protective film forming film is equal to or more than the lower limit value, a protective film having higher protective ability can be formed when the non-curable protective film forming film is used as the protective film. Further, when the thickness of the non-curable protective film forming film is equal to or less than the upper limit value, it is possible to prevent the thickness from becoming excessive.
Here, the "thickness of the non-curable protective film forming film" means the total thickness of the non-curable protective film forming film, for example, the non-curable protective film forming film consisting of a plurality of layers. The thickness means the total thickness of all layers constituting the non-curable protective film forming film.

<< Non-curable protective film forming composition >>
The non-curable protective film-forming film can be formed using the non-curable protective film-forming composition containing the constituent material. For example, by applying the composition for forming a non-curable protective film to the surface to be formed of the film for forming a non-curable protective film, and drying it if necessary, to form a non-curable protective film on the target site. A film can be formed. The content ratio of the components that do not vaporize at room temperature in the non-curable protective film forming composition is usually the same as the content ratio of the components of the non-curable protective film forming film. Here, "normal temperature" is as described above.

  The non-curable protective film-forming composition can be applied, for example, by the same method as in the case of applying the pressure-sensitive adhesive composition described above.

  The drying conditions of the composition for forming a non-curable protective film are not particularly limited, but the composition for forming a non-curable protective film contains a solvent described below, and is preferably dried by heating. For example, it is preferable to dry at 70 ° C. or higher and 130 ° C. or lower for 10 seconds or longer and 5 minutes or shorter.

<Non-curable protective film forming composition (V-1)>
As the composition for forming a non-curable protective film, for example, the composition for forming a non-curable protective film (V-1) containing the non-curable component (c) (in the present specification, simply "composition (V-1) "may be abbreviated) and the like.

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

  The composition (V-1) is selected from the group consisting of a filler, a coupling agent, a cross-linking agent, a colorant, and a general-purpose additive, depending on the purpose, in addition to the non-curable component (c) 1 It may contain two or more species.

  The filler, the coupling agent, the crosslinking agent, the colorant, and the general-purpose additive in the composition (V-1) are the filler (D) and the coupling agent (E) in the composition (III-1), respectively. ), The cross-linking agent (F), the colorant (I) and the general-purpose additive (J).

In the composition (V-1), the filler, the coupling agent, the crosslinking agent, the colorant, and the general-purpose additive may be used alone or in combination of two or more. Well, when two or more kinds are used in combination, their combination and ratio can be arbitrarily selected.
The content of the filler, the coupling agent, the cross-linking agent, the colorant, and the general-purpose additive in the composition (V-1) may be appropriately adjusted according to the purpose and is not particularly limited.

It is preferable that the composition (V-1) further contains a solvent because the handling property thereof is improved by dilution.
Examples of the solvent contained in the composition (V-1) include the same solvents as those in the composition (III-1).
The solvent contained in the composition (V-1) may be only one kind or two or more kinds.

<< Method for producing non-curable protective film forming composition >>
The composition for forming a non-curable protective film such as the composition (V-1) can be obtained by blending each component for constituting the composition.
The order of adding each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting this compounding component in advance, or by diluting any compounding component other than the solvent in advance. Alternatively, the solvent may be used by mixing with these compounding ingredients.
The method of mixing the respective components at the time of compounding is not particularly limited, and a known method such as a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing using a mixer; a method of adding ultrasonic waves to mix It may be selected appropriately.
The temperature and 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 higher and 30 ° C. or lower.

◇ Method for producing protective film forming composite sheet In the protective film forming composite sheet, the width of the protective film forming film with respect to the positional relationship corresponding to each layer described above and the width (maximum length in the TD direction) of the supporting sheet described above. It can be manufactured by sequentially laminating so that the ratio becomes (the maximum length in the TD direction). The method of forming each layer is as described above.

  For example, when a protective film-forming composite sheet is produced, when a protective film-forming film is further laminated on the pressure-sensitive adhesive layer that has already been laminated on the substrate, the thermosetting The protective film forming composition, the energy ray curable protective film forming composition or the non-curable protective film forming composition can be applied to directly form the protective film forming film. As described above, in the case of using any of the compositions to form a continuous two-layer laminated structure, the composition is further applied onto the layer formed from the composition to form a new layer. Can be formed. However, of these two layers, the layer to be laminated later is formed in advance by using the composition on another release film, and the side of the formed layer which is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the exposed surface on the opposite side to the exposed surface of the remaining layer that has already been formed. At this time, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as needed after the laminated structure is formed.

  That is, in the case of producing a composite sheet for forming a protective film, by coating the pressure-sensitive adhesive composition on the substrate, and if necessary dried, to laminate the pressure-sensitive adhesive layer on the substrate, Separately, a thermosetting protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition is applied onto a release film, and dried as necessary. A protective film-forming film is formed on the release film, and the exposed surface of the protective film-forming film is bonded to the exposed surface of the pressure-sensitive adhesive layer already laminated on the base material to form a protective film-forming film. Is laminated on the pressure-sensitive adhesive layer to obtain a composite sheet for forming a protective film.

On the other hand, when laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of coating the pressure-sensitive adhesive composition on the substrate, apply the pressure-sensitive adhesive composition on the release film. The adhesive layer is formed on the release film by drying the adhesive layer if necessary, and the exposed surface of the adhesive layer is attached to one surface of the substrate to form the adhesive layer on the substrate. It may be laminated on top.
In either method, the release film may be removed at any timing after forming the target laminated structure.

  Thus, all layers (adhesive layer, protective film-forming film) other than the base material constituting the protective film-forming composite sheet are pre-formed on the release film, and are then formed on the surface of the target layer. Since the layers can be laminated by a method of laminating, a protective film-forming composite sheet may be manufactured by appropriately selecting a layer adopting such a step as necessary.

  The protective film-forming composite sheet is usually stored in a state where a release film is attached to the surface of the outermost layer (eg, protective film forming film) on the side opposite to the support sheet. Therefore, a thermosetting protective film-forming composition, an energy ray-curable protective film-forming composition, a non-curable protective film-forming composition, or the like on the release film (preferably its release-treated surface), The composition for forming the layer forming the outermost layer is applied, and if necessary, dried to form the layer forming the outermost layer on the release film, and contact with the release film of this layer. It is also possible to laminate the remaining layers on the exposed surface on the side opposite to that on which the protective film is formed by any of the methods described above, and leave the release film in the laminated state without removing the release film. Is obtained.

◇ Method of Using Protective Film Forming Film The protective film forming film of the present invention can be used, for example, in the following method of manufacturing a semiconductor chip with a protective film or a method of manufacturing a semiconductor package.
That is, the protective film-forming film is attached to the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer (FIG. 9B). At this time, the back surface of the semiconductor wafer may be laser-printed in advance (FIG. 9A), or the back surface of the semiconductor wafer may be laser-printed through the protective film forming composite sheet.

Then, the protective film-forming film is heated or irradiated with an energy ray as necessary to cure the protective film-forming film (FIG. 9C) to obtain a protective film. Alternatively, when the film is a protective film-forming film formed from a non-curable protective film-forming composition, it may be used as a protective film as it is uncured. 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 to form a protective film, there is no risk of print deterioration. can do.
Next, a dicing tape is attached to the protective film, and the semiconductor wafer is divided together with the protective film into semiconductor chips. Then, the semiconductor chip is expanded while applying a force from the base material side with the protective film attached (that is, as a semiconductor chip with a protective film) to widen the kerf width between the semiconductor chips, Pick up from the support sheet.
Next, the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate, and then a heat treatment (reflow step) is performed to obtain a semiconductor package (FIG. 9D). Then, a desired semiconductor device may be manufactured using this semiconductor package. By laser-printing on the back surface of the semiconductor wafer instead of laser-printing on the protective film-forming film, there is no fear of print deterioration even by heat treatment (reflow process).
When the protective film-forming film is heated or irradiated with energy rays to be cured, the timing may be before dicing or after dicing, as described above. Above all, it is preferable that the protective film-forming film is heated or irradiated with energy rays to be cured before dicing.

◇ Method of Using Composite Sheet for Forming Protective Film The composite sheet for forming a protective film of the present invention can be used, for example, in the following method for producing a semiconductor chip with a protective film or a method for producing a semiconductor package.
That is, the protective film forming composite sheet is attached to the back surface (the surface opposite to the electrode forming surface) of the semiconductor wafer by the protective film forming film. At this time, the backside of the semiconductor wafer may be laser-printed in advance, or the backside of the semiconductor wafer may be laser-printed through the protective film-forming composite sheet.

Then, the protective film-forming film is heated or irradiated with an energy ray as necessary to cure the protective film-forming film to form a protective film. Alternatively, when the film is a protective film-forming film formed from a non-curable protective film-forming composition, it may be used as a protective film as it is uncured.
Next, the semiconductor wafer is divided by dicing together with the protective film into semiconductor chips. 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 to form a protective film, there is no fear of print deterioration. can do.
After that, the semiconductor chip is separated from the support sheet and picked up by the same method as the method of using the protective film forming film. Next, the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate and then subjected to heat treatment (reflow process) to obtain a semiconductor package. Then, a desired semiconductor device may be manufactured using this semiconductor package. By laser-printing on the back surface of the semiconductor wafer instead of laser-printing on the protective film-forming film, there is no fear of print deterioration even by heat treatment (reflow process).
When the protective film-forming film is heated or irradiated with energy rays to be cured, the timing may be before dicing or after dicing, as described above. Above all, it is preferable that the protective film-forming film is heated or irradiated with energy rays to be cured before the dicing.

◇ Inspection method The inspection method of the present invention comprises 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 back surface of the semiconductor wafer or the semiconductor wafer. A step of inspecting the semiconductor wafer or the semiconductor chip through the protective film formed by adhering the protective film forming film on the back surface of the semiconductor chip obtained by singulation.

  In the step of inspecting, the back surface of the semiconductor wafer or the back surface of a semiconductor chip obtained by dividing the semiconductor wafer into pieces is pasted with the protection film-forming film, and the semiconductor wafer is passed through the protection film. Alternatively, a step of inspecting for laser marking on the semiconductor chip, grinding marks on the back surface of the semiconductor wafer or the semiconductor chip, or foreign matter between the semiconductor wafer or the semiconductor chip and the protective film. Good.

  The inspection method of the present invention comprises a step of laser-printing on the back surface of a semiconductor wafer, a step of sticking a protective film forming film on the back surface of the semiconductor wafer, and a step of sticking the protective film forming film on the back surface of the semiconductor wafer. It may be provided with a step of inspecting the laser-printed marking on the semiconductor wafer through the protective film formed as described above, the step of laser-printing on the back surface of the semiconductor wafer, and the back surface of the semiconductor wafer. A step of sticking a protective film forming film, and a step of inspecting a grinding mark on the back surface of the semiconductor wafer over the protective film formed by sticking the protective film forming film on the back surface of the semiconductor wafer. Which may be provided, a step of laser-printing on the back surface of the semiconductor wafer, and a step of sticking a protective film forming film on the back surface of the semiconductor wafer. A step of inspecting for a foreign substance between the semiconductor wafer and the protective film through the protective film formed by adhering the protective film forming film on the back surface of the semiconductor wafer. Good.

  Further, the inspection method of the present invention comprises 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 semiconductor chip obtained by dividing the semiconductor wafer into pieces. On the back surface, through the protective film formed by affixing the protective film forming film, may be provided with a step of inspecting the laser printing on the semiconductor chip, on the back surface of the semiconductor wafer A step of laser printing, a step of sticking a protective film forming film on the back surface of the semiconductor wafer, and a back surface of the semiconductor chip obtained by dividing the semiconductor wafer into pieces, the protective film forming film being stuck The method may include a step of inspecting a grinding mark on the back surface of the semiconductor chip through the formed protective film, and laser printing is performed 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 protective film forming film attached to the back surface of a semiconductor chip obtained by dividing the semiconductor wafer into pieces. And a step of inspecting the presence or absence of foreign matter between the semiconductor chip and the protective film through the protective film.

Identification method The identification method of the present invention is a semiconductor obtained by laser-printing on the back surface of a semiconductor wafer, attaching a protective film-forming film on the back surface of the semiconductor wafer, and separating the semiconductor wafer into individual pieces. A step of reading the laser-printed print on the semiconductor chip through the protective film formed by adhering the protective film-forming film on the back surface of the chip to identify the type of the semiconductor chip.

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

The components used in the production of the protective film forming composition (III-1) are shown below.
Polymer component (A) -1: Acrylic polymer (weight average molecular weight: 370,000) obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate.
(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: 42 10,000)
Thermosetting component (B1) -1: Bisphenol A epoxy resin (JER828 manufactured by Mitsubishi Chemical, epoxy equivalent 184 to 194 g / eq)
(B1) -2: Bisphenol A-type epoxy resin (JER1055 manufactured by Mitsubishi Chemical, epoxy equivalent 800 to 900 g / eq)
(B1) -3: Dicyclopentadiene type epoxy resin (Epiclon HP-7200HH manufactured by DIC Corporation, epoxy equivalent of 255 to 260 g / eq)
(B2) -1: Thermally active latent epoxy resin curing agent (dicyandiamide (ADEKA HARDNER EH-3636AS manufactured by ADEKA, active hydrogen amount 21 g / eq)) and curing accelerator (C) -1: 2-phenyl-4,5. -Dihydroxymethylimidazole (CUREZOL 2PHZ manufactured by Shikoku Chemicals)

Filler (D) -1: Silica filler (SC2050MA manufactured by Admatechs, average particle diameter 0.5 μm)
(D) -2: Silica filler (manufactured by Tatsumori Co., SV-10, average particle size 8.0 μm) / coupling agent (E) -1: Silane coupling agent (A-1110, manufactured by Nippon Unicar) / colorant

(I) -1: Organic black pigment (6377 black manufactured by Dainichi Seika Kogyo Co., Ltd.)
(I) -2: Carbon black (# MA650, manufactured by Mitsubishi Chemical Corporation, average particle size 28 nm)

[Example 1]
<Production of protective film forming film>
(Production of protective film forming composition (1))
Polymer component (A) -1 (150 parts by mass), thermosetting component (B1) -1 (60 parts by mass), (B1) -2 (10 parts by mass), and (B1) -3 in terms of solid weight ratio. (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 colorant (I) -1 (15 parts by mass) are dissolved or dispersed in methyl ethyl ketone and stirred at 23 ° C. to form a thermosetting protective film. A composition (1) was obtained.

(Manufacturing of protective film forming film (1))
On the release-treated surface of a release film (“SP-PET381031” manufactured by Lintec Co., Ltd., thickness 38 μm) in which one side of a polyethylene terephthalate film was release-treated by silicone treatment, the protective film-forming composition (1 Was coated with a knife coater and dried at 100 ° C. for 2 minutes to prepare a thermosetting protective film-forming film (1) having a thickness of 25 μm.

<Evaluation of protective film forming film>
(Evaluation of image clarity)
Using Suga Test Instruments Co., Ltd. image clarity measuring device "ICM-10P", 5 kinds of slits (slit width: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm and according to JIS K 7374). The total value of 2 mm) was measured as the image definition of the protective film forming film (1). The measurement results are shown in Table 1.

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

(Haze of protective film forming film)
The haze (%) of the protective film-forming film was measured using NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7136: 2000 and using a white LED (5V, 3W) as a light source. . The measurement results are shown in Table 1.

(Surface roughness of protective film forming film)
The surface roughness (Ra) of the film for protective film formation was measured in-plane by using an optical interference type surface profile measuring device (Veeco Metrology Group, product name "WYKO WT1100") at a magnification of 10 times in PSI mode. 10 points were measured and the average value was calculated. The measurement results are shown in Table 1.

(Evaluation of print visibility)
Printing was performed on an 8-inch semiconductor wafer using a laser printing device CSM300M manufactured by EO Technics, and the protective film forming film (1) was attached to the surface. The size of the laser-printed characters was 0.3 mm × 0.2 mm.
When the laser-printed characters were visually observed through the protective film-forming film (1), it was determined whether or not the characters could be visually recognized. The evaluation results are shown in Table 1.
A: Visible clearly B: A little blurred but visible C: Invisible

(Evaluation of reliability of protective film)
The laminate obtained above was unrolled, one of the release films was removed from one side of the protective film forming film, and a # 2000 polished silicon wafer (200 mm diameter, thickness 280 μm) was attached to the tape mounter (Lintec Co., Ltd.). Manufactured by "Adwill RAD-3600F / 12) was applied while heating the exposed surface of the protective film-forming film having the release film on one surface at 70 ° C. Then, the illuminance was 230 mW / cm ² , the light amount was 170 mJ /. The protective film-forming film was cured by irradiating with ultraviolet light under the condition of cm ² , and the protective film was formed on the polished surface of the silicon wafer.

  Then, after removing the other release film from the protective film, a dicing sheet (“Adwill G-562” manufactured by Lintec Co., Ltd.) was attached, and the above-mentioned products were prepared using a dicing device (“DFD651” manufactured by Disco Co., Ltd.). The silicon wafer having the protective film formed thereon was diced into a size of 3 mm × 3 mm to obtain a semiconductor chip with a protective film.

  Next, the semiconductor chip with a protective film obtained above was placed in the following pre-conditions that imitate the process when the semiconductor chip is mounted. That is, after baking the semiconductor chip with a protective film for 20 hours at 125 ° C., it is allowed to absorb moisture under conditions of 85 ° C. and a relative humidity of 85% for 168 hours, and then the semiconductor chip with a protective film immediately after being taken out from the moisture absorbing environment is preheated. It was passed through an IR reflow furnace under the conditions of 160 ° C. and a peak temperature of 260 ° C. three times. Then, 25 pieces of the protective film-attached semiconductor chips that have been subjected to the operations so far were placed in a thermal shock device (“TSE-11-A” manufactured by ESPEC) and held at −65 ° C. for 10 minutes, then at 150 ° C. A cooling / heating cycle of holding for 1 minute was repeated 1000 times.

Next, all the semiconductor chips with a protective film were taken out from the thermal shock device, and the presence or absence of floating or peeling at the joint between the semiconductor chip and the protective film and the presence or absence of cracks in the semiconductor chip were checked using a scanning ultrasonic deep damage device (Sonoscan) It was confirmed by observing the cross section of the semiconductor chip with a protective film, using "D9600 ^™ CSAM" manufactured by Mitsui Chemicals. Then, the number of semiconductor chips with a protective film in which at least one of the above-mentioned floating / peeling and cracks has occurred is counted, and when the number (NG number) is 2 or less, it is judged as a reliability pass (A). The case of 3 or more was judged to be a reliability failure (B). The results are shown in Table 1.

[Example 2]
<Production of protective film forming film>
(Production of protective film forming composition (2))
In the production of the protective film-forming composition (1) of Example 1, (D) -1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass), (D) -2 : Thermosetting composition for protective film formation (2) in the same manner as in Example 1 except that silica filler (TV, SV-10, average particle size 8.0 μm, manufactured by Tatsumori Co., Ltd.) (320 parts by mass) was used. ) Got.

(Production of protective film forming film (2))
In the production of the protective film-forming film of Example 1, the protective film-forming composition (1) was changed to the protective film-forming composition (2) in the same manner as in Example 1 except that the protective film-forming composition (2) was used. A film (2) was obtained.

<Evaluation of protective film forming film>
Using the same method as in Example 1, the image clarity of the protective film forming film (2), the light transmittance at a wavelength of 550 nm, the haze, the surface roughness and the print visibility, and the reliability of the protective film were evaluated. did. The results are shown in Table 1 below. In Example 1 in which the filler diameter is small, the numerical value of the image clarity is large and the visibility is excellent.

[Example 3]
<Production of protective film forming film>
(Production of protective film forming composition (4))
In the production of the protective film forming composition (1) of Example 1, (I) -1: organic black pigment (CF3-4 manufactured by Dainichiseika Kogyo KK) (15 parts by mass) was not used. In the same manner as in Example 1, a thermosetting composition (4) for forming a protective film was obtained.

(Production of protective film forming film (4))
In the production of the protective film-forming film of Example 1, the protective film-forming composition (1) was changed to the protective film-forming composition (4) in the same manner as in Example 1 except that the protective film-forming composition (4) was used. A film (4) was obtained.

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

[Comparative Example 1]
<Production of protective film forming film>
(Production of protective film forming composition (5))
In the production of the protective film forming composition (1) of Example 1, (D) -1: silica filler (SC2050MA manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm) (320 parts by mass) was added to (D) -3. : Silica filler (SC2050MA manufactured by Admatex, average particle size 8.0 μm) (320 parts by mass), (I) -1: Organic black pigment (CF3-4 manufactured by Dainichiseika Kogyo KK) (15 parts by mass) ) Was changed to (I) -3: carbon black (manufactured by Mitsubishi Chemical Corporation, # MA650, average particle size 28 nm) (5.0 parts by mass), in the same manner as in Example 1 except that A composition (5) for forming a protective film was obtained.

(Production of protective film forming film (5))
In the production of the protective film-forming film of Example 1, the protective film-forming composition (1) was changed to the protective film-forming composition (5) in the same manner as in Example 1 except that the protective film-forming composition (5) was used. A film (5) was obtained.

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

[Comparative Example 2]
<Production of protective film forming film>
(Production of protective film forming composition (6))
In the production of the protective film forming composition (1) of Example 1, (D) -1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass) : Silica filler (manufactured by Tatsumori Co., SV-10, average particle size 8.0 μm) (320 parts by mass), (I) -1: Organic black pigment (CF3-4 manufactured by Dainichiseika Kogyo KK) ( 15 parts by mass) was changed to (I) -3: carbon black (manufactured by Mitsubishi Chemical Co., # MA650, average particle size 28 nm) (10.0 parts by mass), and heat was applied in the same manner as in Example 1. A curable protective film forming composition (6) was obtained.

(Production of protective film forming film (6))
In the production of the protective film-forming film of Example 1, the protective film-forming composition (1) was changed to the protective film-forming composition (6) in the same manner as in Example 1 except that the protective film-forming composition (6) was used. A film (6) was obtained.

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

[Example 4]
<Production of protective film forming film>
(Production of protective film forming composition (7))
In the production of the protective film forming composition (1) of Example 1, (D) -1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass) : Thermosetting protective film forming composition (7) was obtained in the same manner as in Example 1 except that silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (10 parts by mass) was used. It was

(Production of protective film forming film (7))
In the process for producing the protective film-forming film of Example 1, the protective film-forming composition (1) was changed to the protective film-forming composition (7) in the same manner as in Example 1 except that the protective film-forming composition (7) was used. A film (7) was obtained.

<Evaluation of protective film forming film>
Using the same method as in Example 1, the image clarity of the protective film-forming film (7), the light transmittance at a wavelength of 550 nm, the haze, the surface roughness and the print visibility, and the reliability of the protective film were evaluated. did. The results are shown in Table 3 below.

[Example 5]
<Production of protective film forming film>
(Production of protective film forming composition (8))
In the production of the protective film forming composition (1) of Example 1, (D) -1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass) : Silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (10 parts by mass), (I) -1: Organic black pigment (6377 black manufactured by Dainichiseika Kogyo KK) (15 parts by mass) A thermosetting protective film-forming composition (8) was obtained in the same manner as in Example 1 except that the above was not used.

(Production of protective film forming film (8))
In the production of the protective film-forming film of Example 1, the protective film-forming composition (1) was changed to the protective film-forming composition (8) in the same manner as in Example 1 except that the protective film-forming composition (8) was used. A film (8) was obtained.

<Evaluation of protective film forming film>
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, the haze, the surface roughness and the print visibility, and the reliability of the protective film were evaluated. did. The results are shown in Table 3 below.

[Example 6]
<Production of protective film forming film>
(Production of protective film forming composition (9))
In the production of the protective film forming composition (1) of Example 1, (I) -1: organic black pigment (6377 black manufactured by Dainichiseika Kogyo KK) (15 parts by mass) was added to (I) -1: A thermosetting composition (9) for forming a protective film was obtained in the same manner as in Example 1 except that the organic black pigment (6377 black manufactured by Dainichiseika Kogyo KK) (32 parts by mass) was used.

(Production of protective film forming film (9))
In the production of the protective film forming film of Example 1, the protective film forming composition (1) was changed to the protective film forming composition (9) in the same manner as in Example 1 except that the protective film forming composition (9) was used. A film (9) was obtained.

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

[Example 7]
<Production of protective film forming film>
(Production of protective film forming composition (10))
In the production of the protective film forming composition (1) of Example 1, the acrylic polymer (A) -1 (weight average molecular weight: 370,000) (150 parts by mass) was added to the acrylic polymer (A) -2. A thermosetting protective film-forming composition (10) was obtained in the same manner as in Example 1 except that the polymer (weight average molecular weight: 420,000) (150 parts by mass) was used.

(Production of protective film forming film (10))
In the production of the protective film-forming film of Example 1, the protective film-forming composition (1) was changed to the protective film-forming composition (10) in the same manner as in Example 1 except that the protective film-forming composition (10) was used. A film (10) was obtained.

<Evaluation of protective film forming film>
Using the same method as in Example 1, the image clarity of the protective film-forming film (10), the light transmittance at a wavelength of 550 nm, the haze, the surface roughness and the print visibility, and the reliability of the protective film were evaluated. did. The results are shown in Table 4 below.

[Comparative Example 3]
<Production of protective film forming film>
(Production of protective film forming composition (11))
In the production of the protective film-forming composition (1) of Example 1, (D) -1: silica filler (SC2050MA manufactured by Admatex, average particle diameter 0.5 μm) (320 parts by mass), (D) -2 : Silica filler (Tatsumori Co., SV-10, average particle diameter 8.0 μm) (320 parts by mass), (I) -1: Organic black pigment (Dainichi Seika Kogyo Co., Ltd. 6377 black) (15) Mass part) was changed to (I) -1: organic black pigment (Dainichi Seika Kogyo Co., Ltd. 6377 black) (32 mass parts) in the same manner as in Example 1 except that the thermosetting protective film was used. A forming composition (11) was obtained.

(Production of protective film forming film (11))
In the production of the protective film-forming film of Example 1, the protective film-forming composition (1) was changed to the protective film-forming composition (11) in the same manner as in Example 1 except that the protective film-forming composition (11) was used. A film (11) was obtained.

<Evaluation of protective film forming film>
Using the same method as in Example 1, the image clarity of the protective film-forming film (11), the light transmittance at a wavelength of 550 nm, the haze, the surface roughness and the print visibility, and the reliability of the protective film were evaluated. did. The results are shown in Table 4 below.

  From Tables 1 to 4, it was clarified that the print visibility was good when the image clarity of the protective film-forming film was 110 or more.

  The protective film-forming film of the present invention is used as it is for sticking to a semiconductor wafer to manufacture a semiconductor device, and as a protective film-forming composite sheet stuck to a supporting sheet such as a dicing tape, it is used as a semiconductor device. It is available for manufacturing.

  Since the image visibility of the protective film-forming film of the present invention is 110 or more, the print visibility is good. Therefore, on the back surface of the semiconductor wafer or the back surface of the semiconductor chip obtained by singulating the semiconductor wafer, The semiconductor wafer or the semiconductor chip can be suitably inspected through the protective film formed by attaching the protective film forming film.

  Further, since the image clarity of the protective film-forming film of the present invention is 110 or more, the print visibility is good. Therefore, the protective film is formed on the back surface of the semiconductor chip obtained by dividing the semiconductor wafer into individual pieces. The type of the semiconductor chip can be suitably identified by reading the laser-printed print on the semiconductor chip through the protective film formed by attaching the forming film.

  1A, 1B, 1C, 1D, 1E, 1F ... Protective film forming composite sheet, 10 ... Support sheet, 10a ... Surface of support sheet (first surface), 11 ... Base material, 11a ... Surface of base material (first surface), 12 ... Adhesive layer, 12a ... Surface of adhesive layer (first surface), 13, 23 ... Film for forming protective film, 13a, 23a ... Surface of protective film forming film (first surface), 13b ... Surface of protective film forming film (second surface), 15 ... Release film, 151 ... First release film, 152 ... Second release film, 16 ... Jig adhesive layer, 16a ... Jig adhesive layer surface, 9 ... Semiconductor wafer

Claims (5)

  A protective film-forming film which is affixed to a laser-printed back surface of a semiconductor wafer and is used for manufacturing a semiconductor chip with a protective film, and which has an image definition of 110 or more.   A composite sheet for forming a protective film, comprising a supporting sheet, and comprising the film for forming a protective film according to claim 1 on the supporting sheet.   Obtained by laser-printing on the back surface of the semiconductor wafer, sticking the protective film-forming film according to claim 1 on the back surface of the semiconductor wafer, and separating the back surface of the semiconductor wafer or the semiconductor wafer into individual pieces. And a step of inspecting the semiconductor wafer or the semiconductor chip through the protective film formed by adhering the protective film forming film on the back surface of the semiconductor chip.   In the step of inspecting, the back surface of the semiconductor wafer or the back surface of a semiconductor chip obtained by dividing the semiconductor wafer into pieces is pasted with the protection film forming film, and the semiconductor wafer is passed through the protection film. Alternatively, it is a step of inspecting the presence or absence of foreign matter between the semiconductor chip and the protective film, laser marking on the semiconductor chip, grinding marks on the back surface of the semiconductor wafer or the semiconductor chip, or the semiconductor wafer or the semiconductor chip. The inspection method according to claim 3.   A step of laser-printing on the back surface of the semiconductor wafer, a step of attaching the protective film forming film according to claim 1 to the back surface of the semiconductor wafer, and a back surface of a semiconductor chip obtained by dividing the semiconductor wafer into individual pieces. A step of reading the laser-printed print on the semiconductor chip through the protective film formed by adhering the protective film-forming film, and identifying the type of the semiconductor chip.

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