JP6298226B1 - Composite sheet for protective film formation - Google Patents

Abstract

Comprising a base material, an adhesive layer and a protective film-forming film laminated on the base material in this order, and having excellent laser printability on a protective film formed from the protective film-forming film; and Provided is a composite sheet for forming a protective film excellent in the visibility of printing of the protective film. The protective film-forming composite sheet includes a base material, and the support layer is a laminate of the base material and the pressure-sensitive adhesive layer, on which the pressure-sensitive adhesive layer and the protective film-forming film are laminated in this order. The haze of the sheet is higher than 45%, and the transmission clearness of the support sheet is 100 or more.

Description

The present invention relates to a composite sheet for forming a protective film.
This application claims priority on March 30, 2017 based on Japanese Patent Application No. 2017-068187 for which it applied to Japan, and uses the content here.

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

  A resin film made of an organic material is formed as a protective film on the exposed back surface of the semiconductor chip, and the semiconductor chip with the protective film obtained by forming the protective film in this way is taken into the semiconductor device. There is. The protective film is used to prevent so-called chipping in which cracks and chips are generated in the semiconductor chip in the steps after the dicing step.

  For the formation of such a protective film, a protective film-forming composite sheet comprising a protective film-forming film on a support sheet is used. As the support sheet, for example, a laminated sheet in which an adhesive layer or the like is laminated on a resin base material is used. In the protective film-forming composite sheet, in addition to the protective film-forming film having a protective film-forming ability, the support sheet can function as a dicing sheet, and the protective film-forming film and the dicing sheet are integrated. It can be made.

On the other hand, in the manufacturing process of a semiconductor device, printing is performed on the surface of the protective film attached to the semiconductor wafer or the semiconductor chip on the support sheet side by irradiation with laser light (referred to as “laser printing” in this specification). May be performed). At this time, the laser light is irradiated through the support sheet from the side opposite to the side where the protective film of the support sheet (base material) is formed. The printing is observed through the support sheet.
Further, in the manufacturing process of the semiconductor device, the state of the semiconductor wafer or the semiconductor chip provided with the protective film forming film or the protective film is inspected by an infrared camera or the like through the support sheet and the protective film forming film or the protective film. There are things to do.
As described above, in the manufacturing process of a semiconductor device, laser printing or observation of a protective film-forming film, a protective film, a semiconductor wafer, or a semiconductor chip may be performed through a support sheet. And the structure of a support sheet has a big influence on the precision of these printing and observation.

  For example, a composite sheet for forming a protective film having high light transmittance and excellent visibility of an image of a semiconductor chip has been disclosed so far in inspection of a semiconductor chip after a dicing process (see Patent Document 1). In the base material constituting the support sheet in the composite sheet for forming a protective film, at least one surface is usually uneven in order to prevent sticking between the base materials when being rolled up, so-called blocking. It is a surface. Then, due to the presence of the uneven surface, the support sheet becomes clouded, and the semiconductor chip including the protective film cannot be clearly observed, and there is a problem that the visibility of the semiconductor chip is poor. On the other hand, in the composite sheet for resin film formation disclosed in Patent Document 1, an adhesive layer is laminated on the concavo-convex surface of the base material, and the haze of the support sheet is 45% or less, thereby supporting The visibility of the semiconductor chip through the sheet is improved.

Japanese Patent No. 5432853

  However, even if the visibility of the semiconductor chip via the support sheet is high, it cannot be said that the laser printability of the protective film via the support sheet is excellent. This is because even if the support sheet enables the visibility of the semiconductor chip to be improved, the laser printing of the protective film and the visual recognition of the print via the support sheet are not always performed satisfactorily. And it is not certain whether the composite sheet for forming a protective film disclosed in Patent Document 1 is also excellent in laser printability.

  Therefore, a substrate is provided, and an adhesive layer and a protective film-forming film are laminated on the base material in this order, and are excellent in laser printability on a protective film formed from the protective film-forming film. In addition, a composite sheet for forming a protective film that is excellent in the visibility of printing of the protective film is provided.

That is, the composite sheet for forming a protective film according to the first aspect of the present invention includes a base material, and an adhesive layer and a film for forming a protective film are laminated on the base material in this order. And the haze of the support sheet which is a laminated body of the said adhesive layer is higher than 45%, and the permeation | transmission definition of the said support sheet is 100 or more.
In the composite sheet for forming a protective film according to the above aspect, the surface of the pressure-sensitive adhesive layer on the side provided with the film for forming a protective film is formed in a region where the film for forming the protective film is not laminated. An adhesive layer may be provided.
The protective film-forming film may be energy ray curable.
The protective film-forming film may be thermosetting.
The protective film-forming film may be non-curable.
The pressure-sensitive adhesive layer may be energy ray curable or non-energy ray curable.
The pressure-sensitive adhesive layer may have a thickness of 3 to 20 μm.
The surface roughness (Ra) of one surface of the base material may be 0.11 μm or more, and the pressure-sensitive adhesive layer may be laminated in direct contact with the surface having the surface roughness.

(1) A base material is provided, and a pressure-sensitive adhesive layer and a protective film-forming film are laminated on the base material in this order, and a haze of a support sheet that is a laminate of the base material and the pressure-sensitive adhesive layer is 45. The composite sheet for forming a protective film, which is higher than% and the transmission sheet has a transmission clarity of 100 or more.
(2) A jig adhesive layer is provided in a region of the pressure-sensitive adhesive layer on the side provided with the protective film-forming film, in a region where the protective film-forming film is not laminated, (1) A composite sheet for forming a protective film as described in 1.
(3) The protective film-forming composite sheet according to (1) or (2), wherein the protective film-forming film is energy ray curable.
(4) The protective film-forming composite sheet according to (1) or (2), wherein the protective film-forming film is thermosetting.
(5) The protective film-forming composite sheet according to (1) or (2), wherein the protective film-forming film is non-curable.
(6) The protective sheet-forming composite sheet according to any one of (1) to (5), wherein the pressure-sensitive adhesive layer is energy ray curable or non-energy curable.
(7) The protective sheet-forming composite sheet according to any one of (1) to (6), wherein the pressure-sensitive adhesive layer has a thickness of 3 to 20 μm.
(8) The surface roughness (Ra) of one surface of the substrate is 0.11 μm or more, and the pressure-sensitive adhesive layer is laminated in direct contact with the surface of the surface roughness, (1) The composite sheet for forming a protective film according to any one of to (7).

  According to the said aspect, it is equipped with a base material, the adhesive layer and the film for protective film formation are laminated | stacked in this order on the said base material, The laser to the protective film formed from the said film for protective film formation There is provided a composite sheet for forming a protective film that has excellent printability and excellent visibility of printed protective film.

FIG. 2 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the first embodiment of the present invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 2nd Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 3rd Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 4th Embodiment of this invention. It is sectional drawing which shows typically the composite sheet for protective film formation which concerns on 5th Embodiment of this invention.

◇ Composite sheet for protective film formation The composite sheet for protective film formation of this embodiment is provided with a base material, and an adhesive layer and a film for protective film formation are laminated on the base material in this order. That is, the protective film-forming composite sheet of this embodiment is formed by laminating a base material, an adhesive layer, and a protective film-forming film in this order. Moreover, in the composite sheet for protective film formation of this embodiment, the haze of the support sheet which is a laminate of the base material and the pressure-sensitive adhesive layer is higher than 45%, and the transparent clarity of the support sheet is 100 or more.
In this specification, the “protective film forming film” means a film before being attached to the back surface of a semiconductor wafer or semiconductor chip, and the “protective film” means a protective film forming film that is a semiconductor wafer or semiconductor. It means the one attached to the back of the chip. In addition, when the protective film-forming film has curability, a film obtained by curing the protective film-forming film is referred to as a “protective film”.
Further, in the present specification, even if the protective film-forming film is attached to a semiconductor wafer or a semiconductor chip, as long as the laminated structure of the support sheet and the protective film-forming film is maintained, this laminated structure Is referred to as a “composite sheet for forming a protective film”.

  The protective film-forming film is used as a protective film for protecting the back surface of the semiconductor wafer or semiconductor chip (the surface opposite to the electrode forming surface). And since the haze of the support sheet is higher than 45% and the transmission sharpness is 100 or more, the protective film-forming film of this embodiment has good laser printability, and printing of the protective film. Visibility can be improved. More specifically, after the protective film-forming composite sheet is attached to the back surface of the semiconductor wafer or semiconductor chip, laser printing is performed on the support sheet side surface of the protective film attached to the semiconductor wafer or semiconductor chip. At this time, the laser light is irradiated through the support sheet from the side opposite to the side on which the protective film of the support sheet (base material) is formed. The printing is observed through the support sheet. At this time, when the transparency of the support sheet is 100 or more, light scattering on the outer surface of the support sheet is suppressed, and the visibility of laser printing can be improved.

Conventionally, in order to increase the thickness of laser printing, it is necessary to perform laser printing at a high output, resulting in a problem of high manufacturing costs. Further, when printing is performed at a high output, there is a possibility that gas accumulation occurs between the protective film and the support sheet when irradiation is performed through the support sheet. Further, by increasing the adhesive strength of the support sheet, it is possible to avoid the accumulation of gas, but there is a problem that the suitability for pickup is impaired. Therefore, it was necessary to perform laser printing directly on the protective film after peeling off the support sheet. On the other hand, in the composite sheet for forming a protective film according to this embodiment, the haze is higher than 45%, so that the laser light is appropriately scattered inside the support sheet. Therefore, the laser printing can be effectively thickened, and the visibility of the laser printing can be improved. Further, since there is no need to increase the laser output, it is possible to suppress the generation of gas accumulation, and it is possible to perform laser printing with the support sheet and the protective film adhered. In addition, since the adhesive strength of the support sheet is appropriate, the pickup suitability is also good.

Furthermore, conventionally, when the adhesive layer for jigs is a colorless and transparent protective film-forming composite sheet, or a protective film-forming composite sheet having no jig adhesive layer, a semiconductor wafer or semiconductor When the composite sheet for forming a protective film is attached to the back surface of the chip with a mounter, the support sheet has a low haze such as 45% or less, and alignment using an optical sensor mounted on the mounter (hereinafter referred to as “position adjustment of the tape tip”). ") Was not possible. On the other hand, in the composite sheet for forming a protective film of the present embodiment, the haze is higher than 45%, so that the position of the tip of the tape can be adjusted by being detected by an optical sensor mounted on the mounter.

The thickness of the semiconductor wafer or semiconductor chip that is the target of use of the composite sheet for forming a protective film of the present embodiment is not particularly limited, but is 30 μm or more and 1000 μm or less because the effect of the present embodiment can be obtained more significantly. It is preferably 100 μm or more and 300 μm or less.
Hereinafter, the configuration of the present embodiment will be described in detail.

Support sheet The support sheet includes a base material, and includes a pressure-sensitive adhesive layer on the base material, and is composed of two or more layers. The constituent materials and thicknesses of these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effects in the present embodiment are not impaired.
In the present specification, not limited to the case of the support sheet, “the plurality of layers may be the same or different from each other” means “all the layers may be the same or all the layers are different. Means that only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and thickness of each layer is different from each other ”. Means.

  Preferable support sheets include, for example, those in which the pressure-sensitive adhesive layer is directly contacted and laminated on the substrate, and those in which the pressure-sensitive adhesive layer is laminated on the substrate via an intermediate layer. More preferable support sheets include those in which an adhesive layer is laminated in direct contact with a substrate.

  An example of the composite sheet for forming a protective film of the present embodiment will be described below for each kind of support sheet with reference to the drawings. Note that the drawings used in the following description may show the main part in an enlarged manner for the sake of convenience in order to make the features of the present embodiment easier to understand. It is not always the same.

FIG. 1 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the first embodiment of the present invention.
The protective film-forming composite sheet 1 </ b> A shown here is provided with a pressure-sensitive adhesive layer 12 on a substrate 11 and a protective film-forming film 13 on the pressure-sensitive adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12. In other words, the protective film forming composite sheet 1 </ b> A has a configuration in which the protective film forming film 13 is laminated on one surface 10 a of the support sheet 10. Further, in the protective film-forming composite sheet 1A, a release film 15 is further laminated on the entire surface (upper surface and side surface) of the surface 13a of the protective film-forming film 13 and the surface 12a (upper surface) of the pressure-sensitive adhesive layer. .
In the present specification, the “peeling film” is a film having a peeling function, and specifically, a protective film forming film for protecting the protective film forming film before being attached to a semiconductor wafer. The film is affixed to the surface of the film and is used by peeling it off during work.

  In the protective film-forming composite sheet 1A, the haze of the support sheet 10 which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 is higher than 45%, and the transparent clarity of the support sheet 10 is 100 or more.

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

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

  The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 1 except that the adhesive sheet 16 for a jig is provided. That is, in the protective film-forming composite sheet 1 </ b> B, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11. The protective film-forming film 13 is laminated on a partial region on the center side of the surface 12a of the pressure-sensitive adhesive layer 12, that is, a semiconductor wafer pasting region. A jig adhesive layer 16 is laminated on a part of the surface 12a of the pressure-sensitive adhesive layer 12, that is, in a region near the peripheral edge. A release film 15 is laminated on the surface 13 a (upper surface) of the protective film forming film 13 and the surface 16 a (upper surface) of the jig adhesive layer 16.

  In the protective film-forming composite sheet 1B, the haze of the support sheet 10 which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 is higher than 45%, and the transmission clearness of the support sheet 10 is 100 or more.

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

  In the protective film-forming composite sheet 1B shown in FIG. 2, the back surface of the semiconductor wafer (not shown) is attached to the front surface 13a of the protective film-forming film 13 with the release film 15 removed. Further, the upper surface of the surface 16a of the jig adhesive layer 16 is used by being attached to a jig such as a ring frame.

FIG. 3 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the third embodiment of the present invention.
The protective sheet-forming composite sheet 1C shown here is the same as the protective film-forming composite sheet 1A shown in FIG. The same thing. In the protective film-forming composite sheet 1 </ b> C, the support sheet 10 is a laminate of the base material 11, the pressure-sensitive adhesive layer 12, and the intermediate layer 17. In other words, the protective film-forming composite sheet 1 </ b> C has a configuration in which the protective film-forming film 13 is laminated on one surface 10 a (17 a) of the support sheet 10. The protective film forming composite sheet 1C further includes the entire surface 13a of the protective film forming film 13 (upper surface and side surface), the surface of the intermediate layer 17a (side surface), and the surface 12a (upper surface) of the adhesive layer. Further, a release film 15 is laminated.

  In the protective film-forming composite sheet 1 </ b> C, the haze of the support sheet 10 that is a laminate of the base material 11, the pressure-sensitive adhesive layer 12, and the intermediate layer 17 is higher than 45%, and the transparent clarity of the support sheet 10 is 100 or more. It is.

  The protective sheet-forming composite sheet 1C shown in FIG. 3 has a semiconductor wafer (not shown) in a partial region on the center side of the surface 13a of the protective film-forming film 13 with the release film 15 removed. The back side is affixed. Furthermore, the area | region of the peripheral part vicinity of the film 13 for protective film formation is affixed and used for jigs, such as a ring frame.

FIG. 4 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the fourth embodiment of the present invention.
The protective sheet-forming composite sheet 1D shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 1 except that the intermediate layer 17 is provided between the base material 11 and the adhesive layer 12. is there. In the protective film-forming composite sheet 1D, the support sheet 10 is a laminate of the base material 11, the intermediate layer 17, and the pressure-sensitive adhesive layer 12. In other words, the protective film-forming composite sheet 1 </ b> D has a configuration in which the protective film-forming film 13 is laminated on one surface 10 a (12 a) of the support sheet 10. The protective film-forming composite sheet 1D further has a release film 15 laminated on the entire surface 13a (upper surface and side surfaces) of the protective film-forming film 13 and the surface 12a (upper surface) of the pressure-sensitive adhesive layer. .

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

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

FIG. 5 is a cross-sectional view schematically showing a protective film-forming composite sheet according to the fifth 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. 2 except that the protective film-forming film is laminated on the entire surface of the pressure-sensitive adhesive layer. . That is, in the protective film forming composite sheet 1 </ b> E, the pressure-sensitive adhesive layer 12 is laminated on one surface 11 a of the substrate 11. A protective film forming film 13 is laminated on the entire surface 12 a of the pressure-sensitive adhesive layer 12. A jig adhesive layer 16 is laminated on a part of the surface 13a of the protective film-forming film 13, that is, in the vicinity of the peripheral edge. A release film 15 is laminated on the surface 13a (upper surface) of the protective film forming film 13 and the surface 16a (upper surface and side surfaces) of the jig adhesive layer 16.

  In the protective sheet-forming composite sheet 1E, the haze of the support sheet 10 which is a laminate of the base material 11 and the pressure-sensitive adhesive layer 12 is higher than 45%, and the transmission clearness of the support sheet 10 is 100 or more.

  In the protective film forming composite sheet 1E shown in FIG. 5, the back surface of the semiconductor wafer (not shown) is attached to the front surface 13a of the protective film forming film 13 with the release film 15 removed. Further, the upper surface of the surface 16a of the jig adhesive layer 16 is used by being attached to a jig such as a ring frame.

  Thus, the protective film-forming composite sheet of the present embodiment may have any form of the support sheet and the protective film-forming film, or may be provided with the jig adhesive layer. However, normally, as shown in FIGS. 2 and 5, as the protective film forming composite sheet of the present embodiment having the jig adhesive layer, the jig is placed on the support sheet 10 or the protective film forming film 13. What provided the adhesive layer 16 for use is preferable.

  The composite sheet for forming a protective film of the present embodiment is not limited to the one shown in FIGS. 1 to 5, and a part of the configuration shown in FIGS. What has been deleted, or what has been added so far, may be added.

For example, in the protective film-forming composite sheet shown in FIGS. 2 and 5, an intermediate layer 17 may be provided between the pressure-sensitive adhesive layer 12 and the protective film-forming film 13. That is, in the composite sheet for forming a protective film of the present embodiment, the support sheet 10 may be formed by laminating the base material 11, the adhesive layer 12, and the intermediate layer 17 in this order. Here, the intermediate layer 17 is the same as the intermediate layer 17 that may be provided in the protective film-forming composite sheet shown in FIGS. Any layer can be selected as the intermediate layer 17 according to the purpose.
For example, in the protective film-forming composite sheet shown in FIGS. 2 and 5, an intermediate layer 17 may be provided between the base material 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for forming a protective film of the present embodiment, the support sheet 10 may be formed by laminating the base material 11, the intermediate layer 17, and the pressure-sensitive adhesive layer 12 in this order. Here, the intermediate layer 17 is the same as the intermediate layer 17 that may be provided in the protective film-forming composite sheet shown in FIGS. Any layer can be selected as the intermediate layer 17 according to the purpose.
Moreover, in the protective film-forming composite sheet shown in FIGS. 1 to 5, the intermediate layer 17 may be provided at other locations other than the locations shown in FIGS. 3 and 4.
In the protective film-forming composite sheet shown in FIGS. 1 to 5, layers other than the intermediate layer 17 may be provided at any location.
Moreover, in the composite sheet for protective film formation shown to FIG. 3 and 4, the adhesive layer 16 for jig | tools may be provided.
Further, in the protective film-forming composite sheet of the present embodiment, a part of the gap may be formed between the release film 15 and the layer in direct contact with the release film 15.
Moreover, in the composite sheet for protective film formation of this embodiment, the magnitude | size and shape of each layer can be arbitrarily adjusted according to the objective.

In the protective sheet-forming composite sheet of the present embodiment, the support sheet may be opaque or colored according to the purpose.
Specifically, the transparent transparency of the support sheet is 100 or more, preferably 150 or more, more preferably 200 or more and 450 or less, and further preferably 300 or more and 430 or less.
When the transparency of the support sheet is in the above range, light scattering on the outer surface of the support sheet is suppressed, and the visibility of laser printing can be improved.
In addition, the transparency of the support sheet can be measured according to JIS K 7374-2007 using an image clarity measuring device “ICM-10P” manufactured by Suga Test Instruments Co., Ltd.
Moreover, what is necessary is just to adjust the surface roughness of the outer surface of a support sheet, for example, in order to make the transmission clarity of a support sheet into the said range.

Further, the haze of the support sheet is higher than 45%, preferably 46% or more, more preferably 47% or more and 90% or less, and further preferably 50% or more and 85% or less.
Conventionally, in order to make laser printing thick, it is necessary to increase the laser output. When irradiation is performed through a support sheet, a gas pool is generated between the protective film and the support sheet. Therefore, it was necessary to perform laser printing directly on the protective film after peeling off the support sheet. In contrast, in the protective film-forming composite sheet of the present embodiment, the laser light is appropriately scattered inside the support sheet because the haze of the support sheet is in the above range. Therefore, the laser printing can be effectively thickened, and the visibility of the laser printing can be improved. Further, it is not necessary to increase the laser output. Therefore, generation of gas pools can be suppressed, and laser printing can be performed with the support sheet and the protective film adhered.

Furthermore, conventionally, when the adhesive layer for jigs is a colorless and transparent protective film-forming composite sheet, or a protective film-forming composite sheet having no jig adhesive layer, a semiconductor wafer or semiconductor When the composite sheet for forming a protective film is attached to the back surface of the chip with a mounter, the support sheet has a low haze such as 45% or less, and alignment using an optical sensor mounted on the mounter (hereinafter referred to as “position adjustment of the tape tip”). ") Was not possible. On the other hand, in the composite sheet for forming a protective film of the present embodiment, the haze of the support sheet is in the above range, so that it can be detected by the optical sensor mounted on the mounter and the position of the tip of the tape can be adjusted.
The haze of the support sheet can be measured according to JIS K 7136-2000 using NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.
Moreover, what is necessary is just to make a base material or an intermediate | middle layer contain a filler or a coloring agent in order to make the haze of a support sheet into the said range, for example. Alternatively, for example, it may be adjusted by changing the hardness of the pressure-sensitive adhesive layer to form a gap between the base material or the intermediate layer and the pressure-sensitive adhesive layer.

Moreover, when the film for protective film formation has energy-beam sclerosis | hardenability, what a transmission sheet permeate | transmits an energy beam is preferable.
For example, in the support sheet, the transmittance measured using an integrating sphere 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, when the protective film forming film is irradiated with energy rays (ultraviolet rays) through the support sheet, the degree of curing of the protective film forming film is further improved.
On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 375 nm is not particularly limited, but may be 95%, for example.

In the present specification, “energy beam curability” means a property of being cured by irradiation with energy rays. “Non-energy radiation curable” means a property that does not cure even when irradiated with energy rays, and includes thermosetting and non-curing properties. “Thermosetting” means a property of being cured by heating. “Non-curing” means the property of not being cured by heating or irradiation with energy rays.
In the present specification, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be emitted by an electron beam accelerator or the like.
Next, each layer which comprises a support sheet is demonstrated in detail.

-Base material The base material is in the form of a sheet or film, and examples of the constituent material include various resins.
Examples of the resin include polyethylenes 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, and norbornene resin. Polyolefin; Ethylene-based copolymer such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as a monomer) A copolymer obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (a resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Naphtha Polyesters such as polyesters, polybutylene terephthalates, polyethylene isophthalates, polyethylene-2,6-naphthalene dicarboxylates, wholly aromatic polyesters in which all the structural units have aromatic cyclic groups; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone;
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.

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

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

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

The thickness of the substrate is preferably 40 μm or more and 300 μm or less, and more preferably 60 μm or more and 150 μm or less. When the thickness of the substrate is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesiveness to a semiconductor wafer or semiconductor chip are further improved.
Here, “the thickness of the substrate” means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate. means. In addition, as a measuring method of the thickness of a base material, the method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.

  The substrate preferably has a high thickness accuracy, that is, a substrate in which variation in thickness is suppressed regardless of the part. Among the above-described constituent materials, examples of materials that can be used to construct such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymers, 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 softener (plasticizer) in addition to the main constituent material such as the resin. May be.
For example, since the base material contains a filler or a colorant, the haze of the support sheet can be within the above range, so that the visibility of laser printing can be improved.

The optical characteristics of the base material only need to satisfy the optical characteristics of the support sheet described above. That is, the substrate may be transparent or opaque, may be colorless or colored according to the purpose, and other layers are processed (for example, vapor deposition). May be.
And when the film for protective film formation has energy-beam sclerosis | hardenability, what a base material permeate | transmits an energy beam is preferable.

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

In the surface-treated substrate, the upper limit value of the surface roughness (Ra) of the surface exposed as the outer surface of the support sheet is 0.60 μm or less, preferably 0.50 μm or less, more preferably 0. .40 μm or less, more preferably 0.30 μm or less. Since the surface roughness of the substrate is less than or equal to the above upper limit value, light scattering on the outer surface of the substrate can be reduced, and the transmission clarity of the support sheet can be within the above range. Can be good.
On the other hand, the lower limit of the surface roughness (Ra) is not particularly limited, and may be, for example, 0.005 μm or more, 0.01 μm or more, or 0.03 μm or more, It may be 0.05 μm or more.
Moreover, when it has a surface whose surface roughness is not more than the above upper limit value and a surface whose surface roughness is 0.11 μm or more, an adhesive layer or the like on the surface whose surface roughness is 0.11 μm or more It is preferable to laminate other layers. Thereby, the surface roughness exposed as the outer surface of the support sheet in the substrate becomes a surface having the upper limit value or less, the light scattering on the outer surface of the substrate is reduced, and the transmission clarity of the support sheet is within the above range. Therefore, the visibility of laser printing can be improved.
When the surface roughness of the substrate is less than or equal to the above upper limit value, another layer such as an adhesive layer is laminated on the surface having a larger surface roughness, and the surface having a smaller surface roughness is the outer surface. As long as it is exposed.
In the present specification, “surface roughness” means a so-called arithmetic average roughness obtained in accordance with JIS B0601: 2001, and is abbreviated as “Ra” unless otherwise specified. .

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

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

  In the present embodiment, the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin. For example, the resin itself has not only an adhesive property. In addition, a resin exhibiting tackiness by using in combination with other components such as additives, a resin exhibiting adhesiveness due to the presence of a trigger such as heat or water, and the like are also included.

  The pressure-sensitive adhesive layer may be composed of one layer (single layer), 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 the multiple layers is not particularly limited.

The thickness of the pressure-sensitive adhesive layer is preferably 3 μm or more and 20 μm or less, more preferably 5 μm or more and 20 μm or less, and particularly preferably 5 μm or more and 17 μm or less.
Adhesive strength can be improved when the thickness of the pressure-sensitive adhesive layer is not less than the above lower limit. Moreover, when it is a base material whose surface roughness is 0.11 micrometer or more, it can be set as the laminated body which embeds the surface of a base material and has a smooth surface where the light scattering of the base-material outer surface was reduced. On the other hand, when the thickness of the pressure-sensitive adhesive layer is not more than the above upper limit value, blade dicing suitability and pickup suitability can be improved.
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. In addition, as a measuring method of the thickness of an adhesive layer, the method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.

  By adjusting the hardness of the pressure-sensitive adhesive layer as appropriate, a gap is formed between the pressure-sensitive adhesive layer and the base material or the intermediate layer, and the haze of the support sheet can be adjusted to be within the above range.

The optical properties of the pressure-sensitive adhesive layer only need to satisfy the optical properties of the support sheet described above. That is, the pressure-sensitive adhesive layer may be opaque or colored according to the purpose.
And when the film for protective film formation has energy-beam sclerosis | hardenability, what the energy layer permeate | transmits an adhesive layer is preferable.

  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 non-energy ray curable adhesive includes a thermosetting adhesive and a non-curable adhesive. The pressure-sensitive adhesive layer formed using the energy ray-curable pressure-sensitive adhesive can easily adjust the physical properties before and after curing.

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

  The adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. And a method using various coaters such as a Meyer bar coater and a kiss coater.

  The drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but the pressure-sensitive adhesive composition is preferably heated and dried when it contains a solvent described later. In this case, for example, the pressure-sensitive adhesive composition is 10 to 70 ° C to 130 ° C. It is preferable to dry on the conditions for 2 seconds or more and 5 minutes or less.

  When the pressure-sensitive adhesive layer is energy ray-curable, the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable pressure-sensitive adhesive composition, for example, non-energy ray-curable pressure-sensitive adhesive A pressure-sensitive adhesive composition (I-1) containing a resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound; Energy-ray-curable adhesive resin (I-2a) (hereinafter referred to as “adhesive resin (I-2a)”) in which an unsaturated group is introduced into the side chain of the linear-curable adhesive resin (I-1a) Pressure-sensitive adhesive composition (I-2) containing the adhesive resin (I-2a) and an energy ray-curable compound (I-3), etc. Is mentioned.

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

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

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

  From the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer, the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester in which the alkyl group has 2 or more carbon atoms. And from the point which the adhesive force of an adhesive layer improves more, it is preferable that carbon number of the said alkyl group is 2-12, and it is more preferable that it is 4-8. In addition, the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.

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

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

  Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic polymers such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.

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

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

  As for the functional group-containing monomer constituting the acrylic polymer, only one type may be used, or two or more types may be used, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

  In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1% by mass or more and 29% by mass or less, and preferably 2% by mass or more and 25% by mass or less with respect to the total amount of the structural unit. It is more preferable that it is 3 mass% or more and 23 mass% or less.

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

The other monomer constituting the acrylic polymer may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

  Only 1 type may be sufficient as the adhesive resin (I-1a) which an adhesive composition (I-1) contains, and when it is 2 or more types, those combinations and ratios are arbitrary. You can choose.

  In the adhesive composition (I-1), the content of the adhesive resin (I-1a) with respect to the total content of all components other than the solvent is preferably 5% by mass or more and 99% by mass or less. More preferably, it is more than 95 mass%, and it is especially preferable that it is 15 mass% or more and 90 mass% or less.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers that have an energy ray-polymerizable unsaturated group and can be cured by irradiation with energy rays.
Among the energy ray curable compounds, examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4. Polyhydric (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 ( And (meth) acrylate.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer from the viewpoint that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly lowered.

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

  In the said adhesive composition (I-1), it is preferable that content of the said energy-beam curable compound with respect to the total content of all components other than a solvent is 1 mass% or more and 95 mass% or less, and 2 masses. % To 90% by mass, more preferably 3% to 85% by mass. For example, 3 mass% or more and 80 mass% or less, 3 mass% or more and 65 mass% or less, 3 mass% or more and 50 mass% or less, 3 mass% or more and 35 mass% or less, etc. may be sufficient.

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

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

  Only 1 type may be sufficient as the crosslinking agent which adhesive composition (I-1) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  In said adhesive composition (I-1), content of a crosslinking agent shall be 0.01 mass part or more and 50 mass parts or less with respect to 100 mass parts of content of adhesive resin (I-1a). Is preferably 0.1 parts by mass or more and 30 parts by mass or less, and particularly preferably 0.3 parts by mass or more and 23 parts by mass or less.

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

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

Only 1 type may be sufficient as the photoinitiator which adhesive composition (I-1) contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

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

[Other additives]
The pressure-sensitive adhesive composition (I-1) may contain other additives that do not correspond to any of the above-described components within a range that does not impair the effects in the present embodiment.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. And known additives such as reaction retarders and crosslinking accelerators (catalysts).
The reaction retarder is, for example, an undesired cross-linking reaction in the preserving adhesive composition (I-1) by the action of the catalyst mixed in the adhesive composition (I-1). It suppresses progress. Examples of the reaction retarder include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C (═O) —) in one molecule. Can be mentioned.

As for the other additive which an adhesive composition (I-1) contains, only 1 type may be sufficient and it may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

[solvent]
The pressure-sensitive adhesive composition (I-1) may contain a solvent. The pressure-sensitive adhesive composition (I-1) contains a solvent, thereby improving the suitability for application to the surface to be coated.

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

As said solvent, you may use as it is in adhesive composition (I-1) as it is, for example, without removing what was used at the time of manufacture of adhesive resin (I-1a) from adhesive resin (I-1a). And the same or different kind of solvent used at the time of manufacture of adhesive resin (I-1a) may be added separately at the time of manufacture of adhesive composition (I-1).

  Only 1 type may be sufficient as the solvent which an adhesive composition (I-1) contains, and when 2 or more types may be sufficient, those combinations and ratios can be selected arbitrarily.

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

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

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

The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by further reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group. A compound having a group.
Examples of the energy ray polymerizable unsaturated group include 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, for example, 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, glycidyl (meth) acrylate, and the like.

  The pressure-sensitive adhesive composition (I-2) contained in the pressure-sensitive adhesive composition (I-2a) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

  In the pressure-sensitive adhesive composition (I-2), the content of the pressure-sensitive adhesive resin (I-2a) with respect to the total content of all components other than the solvent is preferably 5% by mass to 99% by mass. The content is more preferably no less than 95% and no more than 95%, and particularly preferably no less than 10% and no more than 90%.

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

As said crosslinking agent in adhesive composition (I-2), the same thing as the crosslinking agent in adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the crosslinking agent which adhesive composition (I-2) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  In the said adhesive composition (I-2), content of a crosslinking agent shall be 0.01 mass part or more and 25 mass parts or less with respect to 100 mass parts of content of adhesive resin (I-2a). Is more preferably 0.05 parts by mass or more and 20 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 15 parts by mass or less.

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

As said photoinitiator in an adhesive composition (I-2), the same thing as the photoinitiator in an adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the photoinitiator which adhesive composition (I-2) contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

  In adhesive composition (I-2), content of a photoinitiator is 0.01 mass part or more and 20 mass parts or less with respect to 100 mass parts of content of adhesive resin (I-2a). It is preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not correspond to any of the above-described components within a range that does not impair the effects in the present embodiment.
As said other additive in an adhesive composition (I-2), the same thing as the other additive in an adhesive composition (I-1) is mentioned.
As for the other additive which an adhesive composition (I-2) contains, only 1 type may be sufficient and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

[solvent]
The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-2) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
Only 1 type may be sufficient as the solvent which an adhesive composition (I-2) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
In the pressure-sensitive adhesive composition (I-2), the content of the solvent is not particularly limited, and may be adjusted as appropriate.

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

  In the pressure-sensitive adhesive composition (I-3), the content of the pressure-sensitive adhesive resin (I-2a) with respect to the total content of all components other than the solvent is preferably 5% by mass to 99% by mass. More preferably, it is more than 95 mass%, and it is especially preferable that it is 15 mass% or more and 90 mass% or less.

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

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

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

As said photoinitiator in an adhesive composition (I-3), the same thing as the photoinitiator in an adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the photoinitiator which an adhesive composition (I-3) contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

  In the pressure-sensitive adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 mass relative to 100 mass parts of the total content of the pressure-sensitive adhesive resin (I-2a) and the energy ray curable compound. It is preferably no less than 20 parts by mass and no greater than 20 parts by mass, more preferably no less than 0.03 parts by mass and no greater than 10 parts by mass, and particularly preferably no less than 0.05 parts by mass and no greater than 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-3) may contain other additives that do not correspond to any of the above-described components within a range that does not impair the effects in the present embodiment.
As said other additive, the same thing as the other additive in adhesive composition (I-1) is mentioned.
As for the other additive which an adhesive composition (I-3) contains, 1 type may be sufficient, and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

[solvent]
The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-3) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
Only 1 type may be sufficient as the solvent which an adhesive composition (I-3) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
In the pressure-sensitive adhesive composition (I-3), the content of the solvent is not particularly limited, and may be adjusted as appropriate.

<Adhesive composition other than the adhesive compositions (I-1) to (I-3)>
So far, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described. , General pressure-sensitive adhesive compositions other than these three types of pressure-sensitive adhesive compositions (referred to herein as “pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)”) However, it can be used similarly.

Examples of the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions in addition to the energy ray-curable pressure-sensitive adhesive composition.
Non-energy ray curable pressure-sensitive adhesive compositions include, for example, acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. Pressure-sensitive adhesive resin (I-1a) -containing pressure-sensitive adhesive composition (I-4), and those containing an acrylic resin are preferred.

  The pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contains one or more cross-linking agents, and the content thereof is the above-mentioned pressure-sensitive adhesive composition. It can be the same as in the case of (I-1).

<Adhesive composition (I-4)>
As what is preferable with an adhesive composition (I-4), what contains the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-4) include the same ones as the pressure-sensitive adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-1).
The pressure-sensitive adhesive composition (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

  In the pressure-sensitive adhesive composition (I-4), the content of the pressure-sensitive adhesive resin (I-1a) with respect to the total content of all components other than the solvent is preferably 5% by mass to 99% by mass. More preferably, it is more than 95 mass%, and it is especially preferable that it is 15 mass% or more and 90 mass% or less. For example, any of 3 mass% or more and 85 mass% or less, 40 mass% or more and 85 mass% or less, 50 mass% or more and 85 mass% or less, etc. may be sufficient.

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

As a crosslinking agent in adhesive composition (I-4), the same thing as the crosslinking agent in adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the crosslinking agent which adhesive composition (I-4) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  In the said adhesive composition (I-4), content of a crosslinking agent shall be 0.01 mass part or more and 50 mass parts or less with respect to 100 mass parts of content of adhesive resin (I-1a). Is preferably 0.1 parts by mass or more and 50 parts by mass or less, and particularly preferably 1 part by mass or more and 50 parts by mass or less.

[Other additives]
The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-described components within a range that does not impair the effects of the present embodiment.
As said other additive, the same thing as the other additive in adhesive composition (I-1) is mentioned.
As for the other additive which an adhesive composition (I-4) contains, only 1 type may be sufficient and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

[solvent]
The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as that of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-4) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
Only 1 type may be sufficient as the solvent which adhesive composition (I-4) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
In the pressure-sensitive adhesive composition (I-4), the content of the solvent is not particularly limited, and may be adjusted as appropriate.

<< Method for producing pressure-sensitive adhesive composition >>
The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive composition (I-4) It is obtained by blending each component for constituting the pressure-sensitive adhesive composition, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive, if necessary.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

○ Intermediate layer The intermediate layer is in the form of a sheet or film, and its constituent material may be appropriately selected according to the purpose, and is not particularly limited.
Moreover, the haze of the composite sheet for protective film formation can be adjusted to the said range by adjusting the haze of an intermediate | middle layer suitably.
The intermediate layer may be curable or non-curable. Moreover, when an intermediate | middle layer has sclerosis | hardenability, any of thermosetting and energy-beam sclerosis | hardenability may be sufficient.

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

The thickness of the intermediate layer may be, for example, 0.1 μm or more and 200 μm or less, may be 1 μm or more and 150 μm or less, and may be 3 μm or more and 120 μm or less.
Here, “the thickness of the intermediate layer” means the thickness of the entire intermediate layer, and means the total thickness of all the layers constituting the intermediate layer. In addition, as a measuring method of the thickness of an intermediate | middle layer, the method of measuring thickness using a contact-type thickness meter in arbitrary five places, and calculating the average of a measured value etc. are mentioned, for example.

<< Intermediate layer forming composition >>
An intermediate | middle layer can be formed using the composition for intermediate | middle layer formation containing the constituent material.
For example, the intermediate layer can be formed at a target site by applying the intermediate layer-forming composition to the surface on which the intermediate layer is to be formed and drying it as necessary or curing it by irradiation with energy rays.
The intermediate layer-forming composition may be applied by a known method, for example, by the same method as that for the above-mentioned pressure-sensitive adhesive composition.

The drying conditions of the intermediate layer forming composition are not particularly limited. For example, the intermediate layer-forming composition containing a solvent is preferably heat-dried. In this case, for example, it is preferably dried at 70 to 130 ° C. for 10 seconds to 5 minutes.
When the composition for forming an intermediate layer has energy ray curability, it is preferably cured by irradiation with energy rays after drying.

  There is no special limitation as a composition for intermediate | middle layer formation, For example, the thing similar to what was illustrated in the above-mentioned adhesive composition is mentioned.

The composition for forming an intermediate layer may contain other additives that do not correspond to any of the above-described components within a range not impairing the effects of the invention.
As said other additive, the same thing as the other additive in adhesive composition (I-1) is mentioned, for example.
For example, when the composition for forming an intermediate layer contains a filler or a colorant, the haze of the composite sheet for forming a protective film can be adjusted to the above range.

◎ Protective film-forming film The protective film-forming film may be curable or non-curable.
Moreover, when the film for protective film formation has sclerosis | hardenability, any of thermosetting and energy-beam sclerosis | hardenability may be sufficient.

A film for forming a thermosetting protective film Examples of preferable film for forming a thermosetting protective film include those containing a polymer component (A) and a thermosetting component (B). The polymer component (A) is a component that can be regarded as formed by polymerization reaction of the polymerizable compound. The thermosetting component (B) is a component that can undergo a curing (polymerization) reaction using heat as a reaction trigger. In the present embodiment, the polymerization reaction 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 is composed of a plurality of layers, the plurality of layers may be the same as or different from each other. Here, “the plurality of layers may be the same as or different from each other” means the same as in the case of the above-described base material. And when several layers differ from each other, the combination of these several layers is not specifically limited.

The thickness of the thermosetting protective film-forming film is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 75 μm or less, and particularly preferably 5 μm or more and 50 μm or less. When the thickness of the thermosetting protective film-forming film is equal to or more than the lower limit value, a protective film with higher protective ability can be formed. Moreover, when the thickness of the thermosetting protective film-forming film is equal to or less than the upper limit value, an excessive thickness is suppressed.
Here, the “thickness of the thermosetting protective film forming film” means the thickness of the entire thermosetting protective film forming film, for example, a thermosetting protective film forming film composed of a plurality of layers. The thickness means the total thickness of all the layers constituting the thermosetting protective film forming film. The method for measuring the thickness of the thermosetting protective film-forming film includes, for example, a method of measuring the thickness using a contact-type thickness meter at any five locations and calculating the average of the measured values. Can be mentioned.

The curing conditions for applying and curing the thermosetting protective film-forming film on the back surface of the semiconductor wafer are not particularly limited as long as the degree of curing is such that the protective film exhibits its function sufficiently. What is necessary is just to select suitably according to the kind of film for protective film formation.
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 preferred. The heating time during the curing is preferably 0.5 hours or more and 5 hours or less, more preferably 0.5 hours or more and 3 hours or less, and particularly preferably 1 hour or more and 2 hours or less. preferable.

<< The composition for thermosetting protective film formation >>
The film for forming a thermosetting protective film can be formed using a composition for forming a thermosetting protective film containing the constituent materials. For example, the composition for forming a thermosetting protective film is applied to the surface to be formed of the film for forming a thermosetting protective film, and dried as necessary to form a thermosetting protective film on the target site. A film can be formed. The ratio of the content of 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.

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

  The drying conditions of the composition for forming a thermosetting protective film are not particularly limited, but when the composition for forming a thermosetting protective film contains a solvent to be described later, it is preferably dried by heating. For example, the drying is preferably performed at 70 ° C. to 130 ° C. for 10 seconds to 5 minutes.

<Thermosetting protective film forming composition (III-1)>
As the composition for forming a thermosetting protective film, for example, a composition for forming a thermosetting protective film (III-1) containing a polymer component (A) and a thermosetting component (B) (in this specification) May simply be abbreviated as “composition (III-1)”).

[Polymer component (A)]
The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility and the like 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 type, two or more types, or a combination of two or more types. The ratio can be arbitrarily selected.

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

As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, and more preferably from 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is equal to or more than the lower limit, the shape stability (time stability during storage) of the thermosetting protective film-forming film is improved. In addition, when the weight average molecular weight of the acrylic resin is not more than the above 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. Occurrence of voids and the like with the film is further suppressed.
In the present specification, the 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 equal to or higher than the 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. Moreover, adhesive force with the adherend of a protective film improves because Tg of acrylic resin is below the said upper limit.
In the present specification, “glass transition temperature (Tg)” is represented by a value measured with a “differential scanning calorimetry (DSC) measuring device” in accordance with JIS K7121.

  The acrylic resin is selected from, for example, a polymer of one or more (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like. Examples include copolymers of two or more monomers.

Examples of the (meth) acrylic acid ester constituting the acrylic resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) 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 (Uril), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), (meth) (Meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester, such as heptadecyl acrylate and octadecyl (meth) acrylate (stearyl (meth) acrylate), has a chain structure having 1 to 18 carbon atoms;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentanyl;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
(Meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester;
(Meth) acrylic imide;
Glycidyl group-containing (meth) acrylic acid ester such as (meth) acrylic acid glycidyl;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meta ) Hydroxyl-containing (meth) acrylic acid esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate;
Examples thereof include substituted amino group-containing (meth) acrylic esters such as (meth) acrylic acid N-methylaminoethyl. Here, the “substituted amino group” means a group formed by replacing 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, and the like in addition to the (meth) acrylic acid ester. May be obtained by copolymerization.

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

  The acrylic resin may have a functional group that can be bonded 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 cross-linking agent (F) described later, or may be directly bonded to another compound not via the cross-linking agent (F). . When the acrylic resin is bonded to another compound through the functional group, the reliability of the package obtained using the composite sheet for forming a protective film tends to be improved.

  In the present specification, as the polymer component (A), a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as “thermoplastic resin”) is used alone without using an acrylic resin. It 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, and the thermosetting protective film-forming film easily follows the uneven surface of the adherend. The generation of voids and the like may be further suppressed between the protective protective film-forming film.

  The weight average molecular weight of the thermoplastic resin is preferably 1000 or more and 100,000 or less, and more preferably 3000 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., and 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 thermosetting protective film-forming film may be only one type, two or more types, and when two or more types are used, combinations and ratios thereof. Can be chosen arbitrarily.

  In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the polymer component (A) of the film for forming a thermosetting protective film). The content is preferably 5% by mass or more and 85% by mass or less, more preferably 5% by mass or more and 80% by mass or less, regardless of the type of the polymer component (A). For example, any of 5 mass% or more and 65 mass% or less, 5 mass% or more and 50 mass% or less, 10 mass% or more and 35 mass% or less, etc. may be sufficient.

The polymer component (A) may also correspond to the thermosetting component (B). In this embodiment, when the composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) Is considered to contain a polymer component (A) and a thermosetting component (B).

[Thermosetting component (B)]
The thermosetting component (B) is a component for curing a 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 type, two or more types, and when two or more types, Combinations and ratios can be arbitrarily selected.

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

(Epoxy thermosetting resin)
The epoxy thermosetting resin includes an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy thermosetting resin contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, and combinations of two or more types. The ratio can be arbitrarily selected.

・ Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.

  As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an 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 group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
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). An acrylamide group etc. are mentioned, An acryloyl group is preferable.

Although the number average molecular weight of an epoxy resin (B1) is not specifically limited, From the point of sclerosis | hardenability of the film for thermosetting protective film formation, and the intensity | strength and heat resistance of the protective film after hardening, it is 300 or more and 30000 or less. Is more preferably 300 or more and 10,000 or less, and particularly preferably 300 or more and 3000 or less.
In the present specification, the “number average molecular weight” means a number average molecular weight represented by a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

The epoxy equivalent of the epoxy resin (B1) is preferably 100 g / eq or more and 1000 g / eq or less, and more preferably 150 g / eq or more and 950 g / eq or less.
In the present specification, the “epoxy equivalent” means the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236: 2001.

  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).
As a thermosetting agent (B2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene type phenol resins, and aralkyl type phenol resins. .
Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and the aromatic ring of the phenol resin. Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the unsaturated hydrocarbon group described above.

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

Among the thermosetting agents (B2), for example, the number average molecular weight of a resin component such as a polyfunctional phenol resin, a novolac-type phenol resin, a dicyclopentadiene-type phenol resin, or an aralkyl-type phenol resin may be 300 or more and 30000 or less. Preferably, it is 400 or more and 10,000 or less, and particularly preferably 500 or more and 3000 or less.
Of the thermosetting agent (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 or more and 500 or less, for example.

  A thermosetting agent (B2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

  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 with respect to 100 parts by mass of the epoxy resin (B1). The amount is preferably 500 parts by mass or less, and more preferably 1 part by mass or more and 200 parts by mass or less. For example, any of 1 part by mass or more and 100 parts by mass or less, 1 part by mass or more and 50 parts by mass or less, and 1 part by mass or more and 10 parts by mass or less may be used. When the content of the thermosetting agent (B2) is equal to or higher than the lower limit value, the curing of the thermosetting protective film forming film more easily proceeds. Moreover, the moisture absorption rate of the film for thermosetting protective film formation was reduced because the said content of the thermosetting agent (B2) was below the said upper limit, and it was obtained using the composite sheet for protective film formation Improved 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 more preferably 40 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the polymer component (A). It is particularly preferable that the amount is not more than part 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 peelability 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 Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (one or more hydrogen atoms are other than hydrogen atoms) An imidazole substituted with a group of; an organic phosphine such as tributylphosphine, diphenylphosphine, triphenylphosphine (a phosphine having one or more hydrogen atoms substituted with an organic group); 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 type, two or more types, and combinations of two or more types. The ratio can be arbitrarily selected.

  When using a hardening accelerator (C), in composition (III-1) and the film for thermosetting protective film formation, content of a hardening accelerator (C) is content 100 of a thermosetting component (B). It is preferable that it is 0.01 mass part or more and 10 mass parts or less with respect to a mass part, and it is more preferable that it is 0.1 mass part or more and 7 mass parts or less. The effect by using a hardening accelerator (C) is acquired more notably because the said content of a hardening accelerator (C) is more than the said lower limit. Moreover, since content of a hardening accelerator (C) is below the said upper limit, for example, a highly polar hardening accelerator (C) is in a film for thermosetting protective film formation under high temperature and high humidity conditions. The effect of suppressing segregation by moving to the adhesion interface side with the adherend is increased, and the reliability of the semiconductor chip with a protective film obtained using the protective film-forming composite sheet is further improved.

[Filler (D)]
The composition (III-1) and the thermosetting protective film-forming film may contain a filler (D). When the thermosetting protective film-forming film contains the filler (D), the protective film obtained by curing the thermosetting protective film-forming film can easily adjust the thermal expansion coefficient. 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 using the composite sheet for forming the protective film is further improved. Moreover, the moisture absorption rate of a protective film can be reduced or heat dissipation can be improved because the film for thermosetting protective film formation contains a filler (D).

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

  Only 1 type may be sufficient as the filler (D) which the composition (III-1) and the film for thermosetting protective film formation contain, when 2 or more types may be sufficient, The ratio can be arbitrarily selected.

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

[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, the adhesion and adhesion of the thermosetting protective film-forming film to the adherend can be improved. it can. Moreover, the water resistance improves the film | membrane obtained by hardening | curing the film for thermosetting protective film formation by using a coupling agent (E), 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), the thermosetting component (B), etc., and is preferably a silane coupling agent. More preferred.
Preferred examples of the silane coupling agent include 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-mercaptopropi Examples include trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. It is done.

  The coupling agent (E) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, two or more types, or a combination thereof when two or more types are used. The ratio can be arbitrarily selected.

  When the coupling agent (E) is used, in the composition (III-1) and the thermosetting protective film-forming film, the content of the coupling agent (E) is the polymer component (A) and the thermosetting component. It is preferable that it is 0.03 mass part or more and 20 mass parts or less with respect to 100 mass parts of total content of (B), It is more preferable that it is 0.05 mass part or more and 10 mass parts or less, 0.1 It is particularly preferable that the amount is not less than 5 parts by mass. When the content of the coupling agent (E) is equal to or more than the lower limit, the dispersibility of the filler (D) in the resin is improved, and the thermosetting protective film-forming film is adhered to the adherend. The effect by using a coupling agent (E), such as a property improvement, is acquired more notably. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (E) is below the said upper limit.

[Crosslinking agent (F)]
As the polymer component (A), those having functional groups such as vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxy group, isocyanate group and the like that 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 crosslinking agent (F) for bonding the functional group with another compound to crosslink. By crosslinking using the crosslinking agent (F), the initial adhesive force and cohesive force of the thermosetting protective film-forming film can be adjusted.

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

  Examples of the organic polyvalent isocyanate compound include 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 and the like”). A trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc. The “adduct body” includes the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound, or the alicyclic polyvalent isocyanate compound, and a low amount of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, or the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include an xylylene diisocyanate adduct of trimethylolpropane as described later. The “terminal isocyanate urethane prepolymer” is as described above.

  More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 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 is added to all or some hydroxyl groups of a polyol such as propane. 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-aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.

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

  Only 1 type may be sufficient as the crosslinking agent (F) which the composition (III-1) and the film for thermosetting protective film formation contain, and when it is 2 or more types, they are combinations and The ratio can be arbitrarily selected.

  When using a crosslinking agent (F), in composition (III-1), content of a crosslinking agent (F) is 0.01 mass part or more with respect to 100 mass parts of content of a 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. The effect by using a crosslinking agent (F) is acquired more notably because the said content of a crosslinking agent (F) is more than the said lower limit. Moreover, the excessive use of a crosslinking agent (F) is suppressed because the said content of a crosslinking agent (F) is below the said upper limit.

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

The energy beam curable resin (G) is obtained by polymerizing (curing) an energy beam 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, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta ( Chain aliphatic skeleton-containing (meth) acrylates such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; Cyclic aliphatic skeleton-containing (meth) acrylates such as cyclopentanyl di (meth) acrylate; polyalkylene glycol (meth) acrylates 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 30000 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 type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

  In the composition (III-1), the content of the energy beam 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 preferably 10% by mass or more and 85% by mass or less.

[Photopolymerization initiator (H)]
When composition (III-1) contains energy beam curable resin (G), in order to advance the polymerization reaction of energy beam curable resin (G) efficiently, it contains a photopolymerization initiator (H). It 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, benzoin methyl benzoate, and benzoin dimethyl ketal. Benzoin compounds such as acetophenone, acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2, Acylphosphine oxide compounds such as 4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzylphenyl sulfide, 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; 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 include quinone compounds such as 1-chloroanthraquinone; and photosensitizers such as amine.

  Only 1 type may be sufficient as the photoinitiator (H) which a composition (III-1) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  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 with respect to 100 parts by mass of the energy beam curable resin (G). It is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass.

[Colorant (I)]
The composition (III-1) and the thermosetting protective film-forming film may contain a colorant (I).
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, and phthalocyanines. Dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes , Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex 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 pigment include carbon black, cobalt dye, iron dye, chromium dye, titanium dye, vanadium dye, zirconium dye, molybdenum dye, ruthenium dye, platinum dye, ITO ( Indium tin oxide) dyes, ATO (antimony tin oxide) dyes, and the like.

  Only 1 type may be sufficient as the coloring agent (I) which the composition (III-1) and the film for thermosetting protective film formation contain, and when it is 2 or more types, they are combinations and The ratio can be arbitrarily selected.

  When using the colorant (I), 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 when laser printing is performed on the protective film Can be adjusted. Further, 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 or 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, the coloring of the thermosetting protective film-forming film) The content of the agent (I) is preferably 0.1% 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 preferably 5% by mass or less. When the content of the colorant (I) is equal to or more than the lower limit value, the effect of using the colorant (I) is more remarkably obtained. Moreover, the excessive fall of the light transmittance of the film for thermosetting protective film formation is suppressed because the said content of a coloring agent (I) is below the said upper limit.

[General-purpose additive (J)]
The composition (III-1) and the thermosetting protective film-forming film may contain a general-purpose additive (J) within a range not impairing the effects of the present embodiment.
The general-purpose additive (J) may be a known one, and can be arbitrarily selected according to the purpose, and is not particularly limited. Is mentioned.

The general-purpose additive (J) contained in the composition (III-1) and the thermosetting protective film-forming film may be only one type, or two or more types, or a combination thereof when two or more types are used. 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 the solvent has good handleability.
The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. An ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; an amide (a compound having an amide bond) such as dimethylformamide or N-methylpyrrolidone;
Only 1 type may be sufficient as the solvent which composition (III-1) contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

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

<< Method for Producing Thermosetting Protective Film Forming Composition >>
A composition for forming a thermosetting protective film such as the composition (III-1) can be obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 ° C. or higher and 30 ° C. or lower.

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

  The energy ray-curable protective film-forming film may be only one layer (single layer), or may be two or more layers, and when it is a plurality of layers, these layers may be the same or different from each other, The combination of these multiple 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 equal to or more than the lower limit value, a protective film with higher protective ability can be formed. Moreover, when the thickness of the energy ray-curable protective film-forming film is equal to or less than the upper limit, an excessive thickness is suppressed.
Here, “the thickness of the energy ray curable protective film forming film” means the thickness of the entire energy ray curable protective film forming film, for example, the formation of an energy ray curable protective film composed of a plurality of layers. The film thickness means the total thickness of all layers constituting the energy ray-curable protective film-forming film. In addition, as a method for measuring the thickness of the energy ray-curable protective film-forming film, for example, a method of measuring the thickness using a contact-type thickness meter at any five locations and calculating an average of the measured values, etc. Is mentioned.

The curing conditions for forming the protective film by applying the energy ray-curable protective film-forming film to the back surface of the semiconductor wafer and curing it are as long as the degree of curing is such that the protective film can fully perform its function. It does not specifically limit and it should just select suitably according to the kind of film for energy-beam curable protective film formation.
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. Then, the during curing, the amount of the energy ray is preferably 200 mJ / cm ² or more 1000 mJ / cm ² or less.

<< Energy ray-curable protective film-forming composition >>
The film for forming an energy ray curable protective film can be formed using the composition for forming an energy ray curable protective film containing the constituent material. For example, the energy ray curable protective film is applied to the target surface of the film for forming the energy ray curable protective film, and the energy ray curable protection is applied to the target site by applying the composition for forming the energy ray curable protective film and drying it as necessary. A film-forming film can be formed. In the composition for forming an energy ray-curable protective film, the ratio of the contents of components that do not vaporize at room temperature is usually the same as the ratio of the contents of the components of the film for forming an energy ray-curable protective film. . Here, “normal temperature” is as described above.

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

  The drying conditions of the energy ray-curable protective film-forming composition are not particularly limited, but the energy ray-curable protective film-forming composition preferably comprises heat drying when it contains a solvent described later. In this case, for example, drying is preferably performed at 70 ° C. to 130 ° C. for 10 seconds to 5 minutes.

<Composition for forming an energy ray-curable protective film (IV-1)>
As the composition for forming an energy beam curable protective film, for example, the composition for forming an energy beam curable protective film (IV-1) containing the energy beam curable component (a) (in this specification, simply And the like (may be abbreviated as “composition (IV-1)”).

[Energy ray curable component (a)]
The energy ray curable component (a) is a component that is cured by irradiation with energy rays, and imparts film forming property, flexibility, etc. to the film for forming an energy ray curable protective film, and is hard protected 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 80000 to 2000000 and a molecular weight having an energy ray curable group of 100 to 80000. The following compounds (a2) are mentioned. The polymer (a1) may be crosslinked at least partly with a crosslinking agent or may not be crosslinked.

(Polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000)
Examples of the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 or more and 2,000,000 or less include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, Acrylic resin (a1-1) formed by reacting a group that reacts with the functional group and an energy ray curable compound (a12) having an energy ray curable group such as an energy ray curable double bond. It is done.

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

-Acrylic polymer having a functional group (a11)
Examples of the acrylic polymer (a11) having the functional group include those obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to monomers, monomers other than acrylic monomers (non-acrylic monomers) may be copolymerized.
The acrylic polymer (a11) may be a random copolymer or a block copolymer, 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, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic polymers such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.

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

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

  The acrylic monomer having the functional group that constitutes the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. 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. N-butyl acid, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, 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 (meth) acrylate), (meth) acrylic acid Examples include (meth) acrylic acid alkyl esters such as heptadecyl and octadecyl (meth) acrylate (stearyl stearyl (meth) acrylate) in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms. It is done.

  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 aryl ester such as (meth) acrylic acid phenyl ester, etc .; (meth) acrylic acid ester having an aromatic group; non-crosslinkable (meth) acrylamide and Derivatives thereof: (meth) acrylic acid esters having a non-crosslinking tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate are also included. .

  The acrylic monomer which does not have the functional group constituting the acrylic polymer (a11) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; styrene.
The said non-acrylic monomer which comprises the said acrylic polymer (a11) may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

  1 type may be sufficient as the said acrylic polymer (a11) which comprises the said acrylic resin (a1-1), and when it is 2 or more types and they are 2 or more types, those combinations and ratios 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 more preferably 10% by mass or more and 50% by mass or less. Particularly preferred.

Energy beam curable compound (a12)
The energy ray curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). What has a seed | species or more is preferable, and what has an isocyanate group as said group is more preferable. For example, when the energy beam curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

  The energy beam curable compound (a12) preferably has 1 or more and 5 or less energy beam 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 polyisocyanate compound with hydroxyethyl (meth) acrylate;
Examples thereof include an acryloyl monoisocyanate compound obtained by a reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
Among these, it is preferable that the said energy-beam curable compound (a12) is 2-methacryloyloxyethyl isocyanate.

  The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

  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 is further increased. In addition, when the energy ray curable compound (a12) is a monofunctional compound (having one of the groups per 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 of the groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

The polymer (a1) has a weight average molecular weight (Mw) of preferably 100,000 or more and 2,000,000 or less, more preferably 300,000 or more and 1500,000 or less.
Here, the “weight average molecular weight” is as described above.

  In the case where the polymer (a1) is at least partially crosslinked by a crosslinking agent, the polymer (a1) has been 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 the crosslinking agent is polymerized to be crosslinked at the group that reacts with the crosslinking agent, or the energy ray-curable compound ( In the group which reacts with the functional group derived from a12), it may be crosslinked.

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

(Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000)
Examples of the energy ray-curable group having the energy ray-curable group and the compound (a2) having a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond. ) An acryloyl group, a vinyl group, etc. are mentioned.

  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. A phenol resin etc. are mentioned.

Among the compounds (a2), examples of the low molecular weight compound having an energy ray curable group include polyfunctional monomers or oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylate compound include 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, tricyclodecane dimethanol di (meth) acrylate, 1 , 10-decanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, 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) acrylic) Bifunctional (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) acrylate;
Examples include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

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

  The compound (a2) preferably has a weight average molecular weight of 100 or more and 30000 or less, and more preferably 300 or more and 10,000 or less. Here, the “weight average molecular weight” is as described above.

  1 type may be sufficient as the said compound (a2) which the composition (IV-1) and the film for energy-beam curable protective film formation contain, 2 or more types may be sufficient, and when it is 2 or more types, those combination The ratio can be arbitrarily selected.

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

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

  The acrylic polymer (b-1) may be a known one, for example, a homopolymer of one acrylic monomer, or a copolymer of two or more acrylic monomers. Alternatively, it may be a copolymer of one or two or more acrylic monomers and a monomer (non-acrylic monomer) other than one or two or more 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 include hydroxyl group-containing (meth) acrylic acid esters and substituted amino group-containing (meth) acrylic acid esters. Here, the “substituted amino group” is as described above.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n-. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth ) 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 (meth) acrylate), heptadecyl (meth) acrylate, ( Examples include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester, such as octadecyl (meth) acrylate (stearyl (meth) acrylate), 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 esters such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
(Meth) acrylic acid aralkyl esters such as (meth) acrylic acid benzyl;
(Meth) acrylic acid cycloalkenyl esters such as (meth) acrylic acid dicyclopentenyl ester;
Examples include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester.

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

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

Examples of the polymer (b) that is at least partially crosslinked by a crosslinking agent and does not have an energy ray-curable group include those in which a reactive functional group in the polymer (b) has reacted with a crosslinking agent. Can be mentioned.
The reactive functional group may be appropriately selected according to the type of the crosslinking agent and the like, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. In addition, when the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, and the like. 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 in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip.

  Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group. In the case of the acrylic polymer (b-1), those having the reactive functional group as one or both of the acrylic monomer and the non-acrylic monomer mentioned as monomers constituting the polymer. 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 unit constituting the polymer (b) is 1% by mass. It is preferably 20% by mass or less 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 cross-linking becomes a more preferable range in the polymer (b).

  The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is 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, it is 100,000 or more and 1500,000 or less. Here, the “weight average molecular weight” is as described above.

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

  Examples of the composition (IV-1) include those containing any one or both of the polymer (a1) and the compound (a2). And when a composition (IV-1) contains the said compound (a2), it is preferable to also contain the polymer (b) which does not have an energy-beam curable group further, and in this case, further said (a1) It is also preferable to contain. Further, the composition (IV-1) does not contain the compound (a2), and may contain both 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): Content of the said compound (a2) is 10 mass parts or more and 400 mass parts or less with respect to 100 mass parts of total contents of the said polymer (a1) and the polymer (b) which does not have an energy-beam curable group. It is preferable that it 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 beam curable component (a) and the polymer (b) having no energy beam 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) of the energy ray-curable protective film-forming film is 5% by mass or more and 90% by mass or less. It is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass. When the ratio of the content of the energy ray curable component is within such a range, the energy ray curable film of the energy ray curable protective film forming film becomes more favorable.

  Composition (IV-1) is a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general-purpose additive, depending on the purpose, in addition to the energy ray-curable component. You may contain 1 type, 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 the adherend by heating. And the strength of the protective film formed from the energy ray-curable protective film-forming film is also improved.

  Examples of the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant, and general-purpose additive in the composition (IV-1) include heat in the composition (III-1). The same as the curable component (B), filler (D), coupling agent (E), crosslinking 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. And when 2 or more types may be used together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
What is necessary is just to adjust suitably content of the said thermosetting component in a composition (IV-1), a filler, a coupling agent, a crosslinking agent, a photoinitiator, a coloring agent, and a general purpose additive according to the objective. There is no particular limitation.

The composition (IV-1) preferably further contains a solvent since its handleability is improved by dilution.
As a solvent which composition (IV-1) contains, the same thing as the solvent in composition (III-1) is mentioned, for example.
Only 1 type may be sufficient as the solvent which a composition (IV-1) contains, and 2 or more types may be sufficient as it.

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

○ Non-curable protective film-forming film As a preferable non-curable protective film-forming film, for example, a non-curable component (c) is contained. In the film for forming a non-curable protective film, the non-curable component (c) does not have curability, has adhesiveness to the support sheet, and has an appropriate hardness to protect the semiconductor wafer or 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 two or more layers, and when it is a plurality of layers, these layers may be the same or different from each other. The combination of the multiple 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 with higher protective ability can be formed. Moreover, when the thickness of the film for forming a non-curable protective film is equal to or less than the upper limit, an excessive thickness is suppressed.
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, a non-curable protective film-forming film composed of a plurality of layers. The thickness means the total thickness of all the layers constituting the non-curable protective film-forming film. The method for measuring the thickness of the non-curable protective film-forming film includes, for example, a method of measuring the thickness using a contact-type thickness meter at any five locations and calculating the average of the measured values. Can be mentioned.

<< Non-curable protective film forming composition >>
The non-curable protective film-forming film can be formed using a non-curable protective film-forming composition containing the constituent materials. For example, the composition for forming a non-curable protective film is applied to the surface to be formed of the film for forming a non-curable protective film, and is dried as necessary to form a non-curable protective film on the target site. A film can be formed. In the composition for forming a non-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 in the film for forming a non-curable protective film. Here, “normal temperature” is as described above.

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

  The drying conditions for the non-curable protective film-forming composition are not particularly limited, but when the non-curable protective film-forming composition contains a solvent to be described later, it is preferably heat-dried. For example, the drying is preferably performed at 70 ° C. to 130 ° C. for 10 seconds to 5 minutes.

<Non-curable composition for forming protective film (V-1)>
Examples of the non-curable protective film-forming composition include, for example, a non-curable protective film-forming composition (V-1) containing a non-curable component (c) (in this specification, simply “composition ( V-1) ”may be abbreviated as“.

  The non-curable component (c) is a thermoplastic resin, and examples thereof include, but are not limited to, acrylic polymers. As said acrylic polymer, the thing similar to what was illustrated as said acrylic polymer (b-1) is mentioned.

  The composition (V-1) is selected from the group consisting of a filler, a coupling agent, a crosslinking agent, a colorant, and a general-purpose additive in addition to the non-curable component (c). You may contain the seed or two or more sorts.

  Examples of the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive in the composition (V-1) include the filler (D) and the coupling agent (E in the composition (III-1), respectively. ), Crosslinker (F), colorant (I), and general-purpose additive (J).

In the composition (V-1), the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive may be used alone or in combination of two or more. Well, when using 2 or more types together, those combinations and ratios can be arbitrarily selected.
The content of the filler, coupling agent, crosslinking agent, colorant, and general-purpose additive in the composition (V-1) may be appropriately adjusted according to the purpose, and is not particularly limited.

The composition (V-1) preferably further contains a solvent since its handleability is improved by dilution.
As a solvent which a composition (V-1) contains, the same thing as the solvent in a composition (III-1) is mentioned, for example.
Only 1 type may be sufficient as the solvent which a composition (V-1) contains, and 2 or more types may be sufficient as it.

<< Method for producing composition for forming non-curable protective film >>
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 addition at the time of blending 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 the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 ° C. or higher and 30 ° C.

  In one aspect of the present invention, the composite sheet for forming a protective film includes a protective film-forming film containing the following components, an adhesive layer containing the following components, and a substrate having the following configuration: They are stacked in this order.

Specifically, the protective film-forming film is
As the polymer component (A) -1, an acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 35 to 400,000, preferably 370,000) Glass transition temperature: 3 to 9 ° C., preferably 6 ° C.) to 100 to 200 parts by mass, preferably 150 parts by mass;
As epoxy resin (B1) -1, bisphenol A type epoxy resin (epoxy equivalent: 180 to 200 g / eq, preferably 184 to 194 g / eq) is 50 to 70 parts by mass, preferably 60 parts by mass;
As epoxy resin (B1) -2, bisphenol A type epoxy resin (epoxy equivalent: 750 to 950 g / eq, preferably 800 to 900 g / eq) is 5 to 15 parts by mass, preferably 10 parts by mass;
As epoxy resin (B1) -3, dicyclopentadiene type epoxy resin (epoxy equivalent: 250 to 270 g / eq, preferably 255 to 260 g / eq) is 20 to 40 parts by mass, preferably 30 parts by mass;
As thermosetting agent (B2), 1 to 3 parts by mass, preferably 2 parts by mass of thermoactive latent epoxy resin curing agent (dicyandiamide, active hydrogen amount: 20 to 25 g / eq, preferably 21 g / eq);
1-3 parts by mass of 2-phenyl-4,5-dihydroxymethylimidazole as the curing accelerator (C), preferably 2 parts by mass;
As filler (D), silica filler (average particle size: 0.1 to 1 μm, preferably 0.5 μm) is 300 to 340 parts by mass, preferably 320 parts by mass;
As a coupling agent (E), 1 to 3 parts by mass, preferably 2 parts by mass of a silane coupling agent;
As a coloring agent (I), a black pigment is contained 16-20 mass parts, Preferably it contains 18 mass parts.

Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
It contains 35 to 60 parts by mass, preferably 40 to 50 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent.

Specifically, the base material is a polypropylene film having a thickness of 70 to 90 μm, preferably 80 μm. Furthermore, the base is a matte surface (surface roughness (Ra): 0.20 to 1.30 μm, preferably 0.20 to 1.20 μm), and a glossy surface or a fine matte surface (surface roughness (Ra)). : 0.05 to 0.15 μm, preferably 0.10 to 0.15 μm).
In addition, the said adhesive layer is laminated | stacked on the mat | matte surface of a base material.
Alternatively, the base material has a mat surface roughness (Ra) (surface roughness (Ra): 0.30 μm or less, preferably 0.20 μm) and a glossy surface or a fine mat surface (surface roughness (Ra ): 0.05 to 0.15 μm, preferably 0.10 to 0.15 μm), the pressure-sensitive adhesive layer is laminated on the glossy surface or fine mat surface of the substrate.

  In one aspect of the present invention, the composite sheet for forming a protective film includes a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.

Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent;
5-15 mass parts of silicone resin microparticles | fine-particles, Preferably it contains 10 mass parts.

  In one aspect of the present invention, the composite sheet for forming a protective film includes a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.

Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent;
3-30 mass parts of epoxy resins, Preferably it contains 5-25 mass parts.

  In one aspect of the present invention, the composite sheet for forming a protective film includes a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.

Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent;
It contains 3 to 7 parts by mass, preferably 5 parts by mass of a titanium oxide white pigment.

  In one aspect of the present invention, the composite sheet for forming a protective film includes a protective film-forming film containing the above components, a pressure-sensitive adhesive layer containing the following components, and a substrate having the above-described configuration.

Specifically, the adhesive layer is
A pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass) as an acrylic polymer. 90-110 parts by weight, preferably 100 parts by weight;
15 to 25 parts by mass, preferably 20 parts by mass of a trifunctional xylylene diisocyanate crosslinking agent;
5-15 mass parts of acrylic polymer microparticles | fine-particles, Preferably it contains 10 mass parts.

◇ Method for Producing Protective Film Forming Composite Sheet The protective film forming composite sheet can be produced by sequentially laminating the above-described layers so as to have a corresponding positional relationship. The method for forming each layer is as described above.

  For example, when producing a protective sheet-forming composite sheet, if a protective film-forming film is further laminated on the adhesive layer already laminated on the substrate, the thermosetting property is applied on the adhesive layer. A protective film-forming film can be directly formed by applying a protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition. As described above, when a continuous two-layer laminated structure is formed using any of the compositions, the composition is further applied onto the layer formed from the composition to newly form a layer. Can be formed. However, the layer laminated after these two layers is formed in advance using the composition on another release film, and the side of the formed layer that is in contact with the release film is It is preferable to form a continuous two-layer laminated structure by bonding the opposite exposed surface to the exposed surfaces of the remaining layers that have 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 necessary after forming the laminated structure.

  That is, when producing a composite sheet for forming a protective film, a pressure-sensitive adhesive composition is coated on a base material, and dried as necessary, thereby laminating a pressure-sensitive adhesive layer on the base material, Separately, a thermosetting protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition is coated on the release film and dried as necessary. The 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 laminated on the base material. Is laminated on the 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, the pressure-sensitive adhesive composition is applied on the release film. The pressure-sensitive adhesive layer is formed on the release film by drying as required, and the exposed surface of the pressure-sensitive adhesive layer is bonded to one surface of the base material so that the pressure-sensitive adhesive layer is bonded to the base material. It may be laminated on top.
In any method, the release film may be removed at an arbitrary timing after the target laminated structure is formed.

  Thus, all layers (adhesive layer, protective film-forming film) other than the base material constituting the protective film-forming composite sheet are formed in advance on the release film, and on the surface of the target layer. Since lamination can be performed by a method of bonding, a composite film for forming a protective film may be manufactured by appropriately selecting a layer that employs such a process as necessary.

  In addition, the composite sheet for protective film formation is normally stored in the state by which the peeling film was bonded by the surface of the outermost layer (for example, film for protective film formation) on the opposite side to the support sheet. Therefore, on this release film (preferably its release-treated surface), such as a thermosetting protective film-forming composition, an energy ray-curable protective film-forming composition, or a non-curable protective film-forming composition, The composition for forming the layer constituting the outermost layer is applied and dried as necessary, so that the layer constituting the outermost layer is formed on the release film, and this layer is in contact with the release film. A composite sheet for forming a protective film can be obtained by laminating the remaining layers on the exposed surface on the side opposite to the side to be coated by any one of the methods described above and leaving the laminated film bonded without removing the release film. Is obtained.

In the present specification, the “peeling film” is a film having a function of peeling, and specifically, a protective film for protecting the protective film-forming film before being attached to a semiconductor wafer or a support sheet. It refers to a film that is affixed to both surfaces of a forming film, and is used by peeling it off during work.
As the release film, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, Polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A transparent film such as a resin film is used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient. Moreover, the film which colored these, an opaque film, etc. can be used. Examples of the release agent include release agents such as silicone-based, fluorine-based, and long-chain alkyl group-containing carbamates.
The thickness of the release film is usually from 10 μm to 500 μm, preferably from 15 μm to 300 μm, and particularly preferably from 20 μm to 250 μm.
Here, the “thickness of the release film” means the thickness of the entire release film. For example, the thickness of the release film composed of a plurality of layers means the total thickness of all the layers constituting the release film. means. In addition, as a measuring method of the thickness of a peeling film, the method etc. which measure thickness using a contact-type thickness meter in arbitrary five places, and calculate the average of a measured value, etc. are mentioned, for example.

◇ Method for Using Protective Film Forming Composite Sheet The protective film forming composite sheet of the present embodiment can be used, for example, by the following method.
That is, the protective film-forming composite sheet is attached to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer with the protective film-forming film. Next, the protective film-forming film is heated or irradiated with energy rays as necessary to cure the protective film-forming film to form a protective film. Or when it is the composition for non-curable protective film formation contained in the film for protective film formation, you may use it as a protective film with uncured. Next, the semiconductor wafer is divided together with the protective film by dicing to form semiconductor chips. Then, the semiconductor chip is picked up while being separated from the support sheet while the protective film is attached (that is, as a semiconductor chip with a protective film).
Thereafter, the semiconductor chip of the obtained semiconductor chip with a protective film is flip-chip connected to the circuit surface of the substrate in the same manner as the conventional method, and then the semiconductor package is obtained. Then, a target semiconductor device may be manufactured using this semiconductor package.
In addition, when hardening the film for protective film formation by heating or irradiating an energy ray, the timing may be before dicing as mentioned above, and may be after dicing. Especially, it is preferable that the timing which cures the film for protective film formation by heating or irradiating an energy ray is before dicing.
When the protective film-forming film is cured by heating or irradiation with energy rays, the timing of laser printing may be before curing or after curing. In particular, when the protective film-forming film is heated and cured, the timing of laser printing is preferably after curing.

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

The components used for the production of the protective film-forming composition are shown below.
Polymer component (A) -1: Acrylic polymer obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 370,000, glass transition temperature: 6 ° C.)
Thermosetting component (B1) -1: Bisphenol A type epoxy resin (Mitsubishi Chemical jER828, epoxy equivalent 184 to 194 g / eq)
(B1) -2: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation jER1055, epoxy equivalent 800-900 g / eq)
(B1) -3: dicyclopentadiene type epoxy resin (Dainippon Ink & Chemicals, Inc. Epicron HP-7200HH, epoxy equivalent 255-260 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))
Curing accelerator (C) -1: 2-phenyl-4,5-dihydroxymethylimidazole (Curesol 2PHZ manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Filler (D) -1: Silica filler (SC2050MA manufactured by Admatechs, average particle size 0.5 μm)
Coupling agent (E) -1: Silane coupling agent (A-1110 manufactured by Nihon Unicar)
Colorant (I) -1: Black pigment (manufactured by Dainichi Seika)

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

(Production of pressure-sensitive adhesive composition (I-4) -1)
Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)), and methyl ethyl ketone as a solvent Non-energy ray-curable pressure-sensitive adhesive composition (I-4) -1 containing a mixed solvent of toluene and ethyl acetate and having a solid content concentration of 30% by mass was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxylethyl acrylate (HEA) (20 parts by mass). is there.

(Manufacture of support sheet)
The pressure-sensitive adhesive composition (I-4) -1 obtained above was applied to the release-treated surface of a release film obtained by subjecting one side of a polyethylene terephthalate film to a release treatment by silicone treatment. A non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 15 μm was formed by heat drying for a few minutes.
Next, an 80 μm-thick polypropylene film (Mitsubishi Resin, mat surface (surface roughness (Ra): 1.20 μm) / shiny surface (surface roughness (Ra): 0) is formed on the exposed surface of the pressure-sensitive adhesive layer. .10 μm) Substrate) was bonded together to produce a support sheet (10) -1.

(Manufacture of composite sheet for protective film formation)
A protective film-forming composition (III) obtained above was applied to the release-treated surface of a release film (“SP-PET 381031” manufactured by Lintec Corporation, thickness 38 μm) from which one side of a polyethylene terephthalate film was subjected to release treatment by silicone treatment. -1) was coated with a knife coater and dried at 100 ° C. for 2 minutes to prepare a thermosetting protective film-forming film (13) -1 having a thickness of 25 μm.

  Next, the exposed surface of the protective film-forming film (13) -1 obtained above is bonded to the pressure-sensitive adhesive layer of the support sheet (10) -1 obtained above, and the base material, the pressure-sensitive adhesive layer, And the protective film formation film (13) -1 produced the composite sheet for protective film formation formed by laminating | stacking in this order in these thickness directions. In the produced protective film-forming composite sheet, the width of the support sheet was 270 mm, and the outer diameter of the protective film-forming film was 210 mm.

<Evaluation of support sheet>
(Haze evaluation)
Using “NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd., it was measured according to JIS K 7136-2000. In addition, it measured by the structure of "the base material + adhesive layer" which peeled the peeling film from the support sheet (10) -1. The results are shown in Table 1.

(Evaluation of transmission clarity)
The measurement was performed in accordance with JIS K 7374-2007 using Suga Test Instruments Co., Ltd. image clarity measuring instrument “ICM-10P”. The total value of five types of slits (slit widths: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm) was expressed as transmission sharpness. In addition, it measured by the structure of "the base material + adhesive layer" which peeled the peeling film from the support sheet (10) -1. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
(Mounter suitability (evaluation of alignment (adjustment of tape tip position))
With respect to the produced protective film-forming composite sheet and ring frame, it was confirmed that the tape tip position could be adjusted using a Lintec tape mounter RAD2700 on an 8-inch semiconductor wafer (thickness: 200 μm). The results are shown in Table 1.
The evaluation criteria for mounter suitability were set as follows.
A ... Alignable B ... Unalignable

(Evaluation of laser printing visibility)
The protective film-forming film affixed to an 8-inch semiconductor wafer is printed on the protective film layer over the support sheet using the laser printing apparatus CSM300M manufactured by EO Technics, and characters can be visually recognized when visually observed. It was determined whether or not. Printing was performed on the uncured protective film layer. The character size was 0.3 mm × 0.2 mm. The results are shown in Table 1.
The evaluation criteria for laser printing visibility were set as follows.
A ... Visible B ... Slightly blurred but visible C ... Not visible

(Evaluation of print character thickness)
For the protective film-forming film affixed to an 8-inch semiconductor wafer, using a UV irradiation device (Rintec Corporation, RAD 2000 m / 8, irradiation conditions: illuminance 195 mW / cm ² , light quantity 170 mJ / cm ² ) Were irradiated with ultraviolet rays. Subsequently, after peeling off the support sheet from the protective film, the print on the protective film was observed with an optical microscope manufactured by Keyence, and the thickness of the characters was measured. The results are shown in Table 1.

[Example 2]
<Manufacture of composite sheet for forming protective film>
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-4) -2)
Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (50 parts by mass (solid content)), and methyl ethyl ketone as a solvent A non-energy ray-curable pressure-sensitive adhesive composition (I-4) -2 having a solid content concentration of 30% by mass was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)
A support sheet (10) -2 was prepared in the same manner as in Example 1 except that the adhesive composition (I-4) -2 was used instead of the adhesive composition (I-4) -1. Obtained.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -2 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Example 3]
<Manufacture of composite sheet for forming protective film>
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-4) -1)
Using the same method as in Example 1, pressure-sensitive adhesive composition (I-4) -1 was obtained.

(Manufacture of support sheet)
On the exposed surface of the pressure-sensitive adhesive layer, a polypropylene film having a thickness of 80 μm (Mitsubishi Resin, mat surface (surface roughness (Ra): 1.20 μm) / shiny surface (surface roughness (Ra): 0.10 μm)) Instead of the mat surface of the base material, a polypropylene film having a thickness of 80 μm (manufactured by Gunze Co., Ltd., mat surface (surface roughness (Ra): 0.20 μm) / fine mat surface (surface roughness (Ra): 0. 0). 15 [mu] m) A support sheet (10) -3 was produced in the same manner as in Example 1 except that the mat surface of the base material) was bonded.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -3 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Example 4]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-4) -3)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based cross-linking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (20 parts by mass (solid content)), and silicone resin fine particles (manufactured by Tanac Corporation) "Tospearl 145") (10 parts by mass (solid content)), further containing methyl ethyl ketone as a solvent, a solid content concentration of 30% by mass, a non-energy ray-curable pressure-sensitive adhesive composition (I-4)- 3 was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)
A support sheet (10) -4 was prepared in the same manner as in Example 1 except that the adhesive composition (I-4) -3 was used instead of the adhesive composition (I-4) -1. Obtained.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -4 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Example 5]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-1) -1)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (20 parts by mass (solid content)), and epoxy resin (manufactured by Mitsubishi Chemical Corporation) "JER834") (25 parts by mass (solid content)), further containing methyl ethyl ketone as a solvent, and an energy ray-curable pressure-sensitive adhesive composition (I-1) -1 having a solid content concentration of 30% by mass Prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)
A support sheet (10) -5 was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (I-1) -1 was used instead of the pressure-sensitive adhesive composition (I-4) -1. Obtained.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -5 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Example 6]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-1) -2)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Takeda Chemicals, Ltd.) (20 parts by mass (solid content)), and epoxy resin (manufactured by Mitsubishi Chemical Corporation) "JER1055") (5 parts by mass (solid content)) and further containing methyl ethyl ketone as a solvent, and an energy ray-curable pressure-sensitive adhesive composition (I-1) -2 having a solid content concentration of 30% by mass Prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)
A support sheet (10) -6 was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (I-1) -2 was used instead of the pressure-sensitive adhesive composition (I-4) -1. Obtained.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -6 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Example 7]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-4) -4)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and titanium oxide white pigment (large Nissei Kasei Co., Ltd. “N-DYM8054”) (5 parts by mass (solid content)), further containing methyl ethyl ketone as a solvent, and a solid content concentration of 30% by mass, a non-energy ray curable pressure-sensitive adhesive composition ( I-4) -4 was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)
A support sheet (10) -7 was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (I-4) -4 was used instead of the pressure-sensitive adhesive composition (I-4) -1. Obtained.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -7 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Example 8]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-4) -5)
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based cross-linking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass (solid content)), and acrylic polymer fine particles (Daisensei) Non-energy ray-curable pressure-sensitive adhesive composition having a solid content concentration of 30% by mass, containing “215 (MD) white” (10 parts by mass (solid content)) and further containing methyl ethyl ketone as a solvent. (I-4) -5 was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)
A support sheet (10) -8 was prepared using the same method as in Example 1 except that the adhesive composition (I-4) -5 was used instead of the adhesive composition (I-4) -1. Obtained.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -8 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Example 9]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

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

(Manufacture of support sheet)
Instead of the pressure-sensitive adhesive composition (I-4) -1, the pressure-sensitive adhesive composition (I-4) -2 was used. On the exposed surface of the pressure-sensitive adhesive layer, a polypropylene film having a thickness of 80 μm (manufactured by Mitsubishi Plastics, Instead of the matte surface of mat surface (surface roughness (Ra): 1.20 μm) / gloss surface (surface roughness (Ra): 0.10 μm)), a 80 μm thick polypropylene film (manufactured by Gunze) The mat surface (surface roughness (Ra): 0.20 μm) / fine mat surface (surface roughness (Ra): 0.15 μm)) is the same as in Example 1 except that the mat surface is bonded. The support sheet (10) -9 was obtained using the method.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -9 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Example 10]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

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

(Manufacture of support sheet)
Instead of the pressure-sensitive adhesive composition (I-4) -1, the pressure-sensitive adhesive composition (I-4) -2 was used. On the exposed surface of the pressure-sensitive adhesive layer, a polypropylene film having a thickness of 80 μm (manufactured by Mitsubishi Plastics, Instead of the matte surface of mat surface (surface roughness (Ra): 1.20 μm) / gloss surface (surface roughness (Ra): 0.10 μm)), a 80 μm thick polypropylene film (manufactured by Gunze) The same as in Example 1 except that the mat surface (surface roughness (Ra): 0.20 μm) / fine mat surface (surface roughness (Ra): 0.15 μm) substrate) was bonded together. Using the method, a support sheet (10) -10 was obtained.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -10 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Comparative Example 1]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-4) -1)
Using the same method as in Example 1, pressure-sensitive adhesive composition (I-4) -1 was obtained.

(Manufacture of support sheet)
A support sheet (10) -9 was produced in the same manner as in Example 1 except that a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 μm was formed instead of the thickness of 15 μm.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -9 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Comparative Example 2]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-4) -6)
Contains acrylic polymer (100 parts by mass, solid content) and trifunctional xylylene diisocyanate crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (30 parts by mass (solid content)), and methyl ethyl ketone as a solvent A non-energy ray-curable pressure-sensitive adhesive composition (I-4) -6 having a solid content concentration of 30% by mass was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)
Except having used adhesive composition (I-4) -6 instead of adhesive composition (I-4) -1, using the method similar to Example 1, support sheet (10) -10 is attached. Obtained.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -10 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Comparative Example 3]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

(Production of pressure-sensitive adhesive composition (I-4) -7)
Contains acrylic polymer (100 parts by mass, solid content) and trifunctional xylylene diisocyanate-based cross-linking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (5 parts by mass (solid content)), and methyl ethyl ketone as a solvent And a non-energy ray-curable pressure-sensitive adhesive composition (I-4) -7 having a solid content concentration of 30% by mass was prepared. The acrylic polymer is a pre-copolymer having a weight average molecular weight of 800,000 obtained by copolymerizing 2EHA (80 parts by mass) and HEA (20 parts by mass).

(Manufacture of support sheet)
The pressure-sensitive adhesive composition (I-4) -7 obtained above is applied to the release-treated surface of a release film obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and the film is heated at 120 ° C. A non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 μm was formed by heat-drying for 5 minutes.
Next, an 80 μm-thick polypropylene film (Mitsubishi Resin, mat surface (surface roughness (Ra): 0.50 μm) / shiny surface (surface roughness (Ra): 0) is formed on the exposed surface of the adhesive layer. .10 μm) The support sheet (10) -11 was manufactured by pasting the glossy surface of the base material).

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -11 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Comparative Example 4]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

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

(Manufacture of support sheet)
A support sheet (10) -12 was prepared using the same method as in Example 1 except that the adhesive composition (I-4) -7 was used instead of the adhesive composition (I-4) -1. Obtained.

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -12 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

[Comparative Example 5]
(Production of protective film-forming composition (III-1))
A thermosetting protective film-forming composition (III-1) was obtained using the same method as in Example 1.

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

(Manufacture of support sheet)
The pressure-sensitive adhesive composition (I-4) -7 obtained above is applied to the release-treated surface of a release film obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and the film is heated at 120 ° C. A non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 μm was formed by heat-drying for 5 minutes.
Next, a 60 μm-thick polypropylene film (manufactured by Riken Technos Co., Ltd., mat surface (surface roughness (Ra): 0.50 μm) / shiny surface (surface roughness (Ra): 0. A support sheet (10) -13 was produced by laminating the glossy surface of the substrate (10 μm).

(Manufacture of composite sheet for protective film formation)
A composite sheet for forming a protective film was produced in the same manner as in Example 1 except that (10) -13 was used instead of the support sheet (10) -1.

<Evaluation of support sheet>
Using the same method as in Example 1, haze and transmission sharpness were evaluated. The results are shown in Table 1.

<Evaluation of composite sheet for forming protective film>
Using the same method as in Example 1, mounter suitability, laser printing visibility, and printed character thickness were evaluated. The results are shown in Table 1.

In Table 1, regarding the pass / fail judgment, the mounter suitability was A evaluation, the laser print visibility was A or B evaluation, and “other” was “No”.
From Table 1, the mounter suitability was A evaluation when the haze of the support sheet was 46% or more. This is because the haze of the support sheet has a certain degree of turbidity (cloudiness) of 46% or more, so that the tip position of the support sheet can be detected by laser irradiation in an optical sensor for adjusting the position of the tip of the tape. It was guessed that this was because it was made.

  Also, from Table 1, when the haze of the support sheet is 46% or more and the transmission sharpness is 100 or more, when the laser printing visibility is B evaluation or more and 200 or more, the laser printing visibility is A evaluation. It was. It was speculated that this was because the visibility of laser printing was improved by suppressing light scattering on the outer surface of the substrate located on the bottom surface of the support sheet. Furthermore, since the haze of the support sheet is 46% or more and has a certain degree of turbidity (cloudiness), the laser light can be appropriately scattered inside the support sheet to increase the thickness of the printed characters. It was assumed that it was because it contributed to the improvement of the visibility of printing.

  From the above, the composite sheet for forming a protective film has excellent laser printability on the protective film and excellent visibility of the printed protective film by adjusting the haze and transmission clarity of the support sheet to an appropriate range. It became clear that

The present invention can be used for manufacturing semiconductor devices.

1A, 1B, 1C, 1D, 1E ... Composite sheet for protective film formation, 10 ... Support sheet, 10a ... Surface of support sheet, 11 ... Base material, 11a ... Surface of base material , 12 ... adhesive layer, 12a ... surface of the adhesive layer, 13 ... protective film forming film, 13a ... surface of protective film forming film, 15 ... release film, 16. ..Jig adhesive layer, 16a ... surface of jig adhesive layer, 17 ... intermediate layer, 17a ... surface of intermediate layer

Claims (8)

Provided with a base material, on the base material, a pressure-sensitive adhesive layer and a protective film-forming film are laminated in this order,
The haze of the support sheet which is a laminate of the base material and the pressure-sensitive adhesive layer is higher than 45%,
A composite sheet for forming a protective film, wherein the support sheet has a transmission clarity of 100 or more.   The jig | tool adhesive layer is provided in the area | region where the said film for protective film formation is not laminated | stacked among the surfaces of the side provided with the said film for protective film formation of the said adhesive layer. Composite sheet for protective film formation.   The composite sheet for forming a protective film according to claim 1 or 2, wherein the protective film-forming film is energy ray curable.   The composite sheet for forming a protective film according to claim 1, wherein the protective film-forming film is thermosetting.   The composite sheet for forming a protective film according to claim 1, wherein the protective film-forming film is non-curable.   The composite sheet for protective film formation according to any one of claims 1 to 5, wherein the pressure-sensitive adhesive layer is energy ray curable or non-energy curable.   The composite sheet for protective film formation as described in any one of Claims 1-6 whose thickness of the said adhesive layer is 3-20 micrometers.   The surface roughness (Ra) of one surface of the base material is 0.11 μm or more, and the pressure-sensitive adhesive layer is laminated in direct contact with the surface of the surface roughness. The composite sheet for forming a protective film according to any one of the above.

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