KR20200138155A - Support sheet and manufacturing method thereof, and composite sheet for forming protective film and manufacturing method thereof - Google Patents

Abstract

This support sheet is a support sheet provided with a base material and a pressure-sensitive adhesive layer on the base material, wherein the side surface of the pressure-sensitive adhesive layer of the base material is an uneven surface, and a test piece is cut out from five places of the support sheet, and these five test pieces WHEREIN: When the cross section of an adhesive layer is observed, the maximum value (d1) of the interlayer distance between the said base material and said adhesive layer is 0.5 micrometers or less. The composite sheet for forming a protective film is provided with a film for forming a protective film on the pressure-sensitive adhesive layer in this supporting sheet.

Description

Support sheet and manufacturing method thereof, and composite sheet for forming protective film and manufacturing method thereof

The present invention relates to a supporting sheet and a method for manufacturing the same, and a composite sheet for forming a protective film and a method for manufacturing the same.

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

On the back surface of the exposed semiconductor chip, a resin film containing an organic material is formed as a protective film, and the protective film is sometimes introduced into a semiconductor device as a semiconductor chip. The protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing process or packaging.

Such a protective film is formed, for example, by curing a film for forming a protective film having curability. In addition, a film for forming a non-curable protective film with controlled physical properties may be used as a protective film as it is. In addition, the film for forming a protective film is affixed to the back surface of a semiconductor wafer and used. The protective film-forming film may be affixed to the back surface of the semiconductor wafer in the form of a composite sheet for forming a protective film integrated with the support sheet used for processing the semiconductor wafer, for example, or the semiconductor wafer in a state that is not integrated with the support sheet. It is also attached to the back side of.

After the protective film-forming composite sheet is affixed to the back surface of the semiconductor chip with the protective film-forming film therein, the protective film is formed by curing the protective film-forming film at appropriate timing, the protective film-forming film or the protective film is cut, Separation (dicing) of a semiconductor wafer into a semiconductor chip, a film for forming a protective film after cutting, or a semiconductor chip with a protective film on the back surface (a semiconductor chip with a film for forming a protective film or a semiconductor chip with a protective film) from the support sheet Etc. are done appropriately. When the semiconductor chip on which the protective film-forming film is formed is picked up, this becomes a semiconductor chip on which the protective film is formed by curing the protective film-forming film, and finally, a semiconductor device is manufactured using the semiconductor chip on which the protective film is formed. Thus, the support sheet in the composite sheet for forming a protective film can be used as a dicing sheet. On the other hand, when the film for forming a protective film is non-curable, in each of these steps, the film for forming a protective film is treated as it is as a protective film.

On the other hand, after the protective film-forming film is affixed to the back surface of the semiconductor wafer in a state that is not integrated with the support sheet, the support sheet is affixed to the exposed surface of the protective film-forming film on the opposite side to the affixed surface of the semiconductor wafer. Thereafter, a semiconductor chip having a protective film formed thereon or a semiconductor chip having a protective film forming film formed thereon is obtained in the same manner as in the case of using the composite sheet for forming a protective film, and a semiconductor device is manufactured. In this case, the film for forming a protective film is affixed on the back surface of the semiconductor wafer in a state that is not integrated with the support sheet, but the composite sheet for forming a protective film is formed by integration with the support sheet after the affixing.

As such a composite sheet for forming a protective film, for example, a dicing tape (support sheet) having a substrate having an uneven surface and an adhesive layer laminated on the uneven surface side of the substrate, and on the adhesive layer of the dicing tape A dicing tape-integrated semiconductor back surface protective film (composite sheet for forming a protective film) having a dicing tape-integrated semiconductor back surface protective film (film for forming a protective film) laminated on the dicing tape, wherein the dicing tape has a haze of 45% or less. A film is disclosed (refer to Patent Document 1).

However, in the composite sheet for forming a protective film disclosed in Patent Document 1 (a dicing tape-integrated semiconductor back surface protective film), the adhesive layer is laminated on the uneven surface side of the substrate, so that the adhesive does not sufficiently follow the irregularities of the substrate. In some cases, a region that is not bonded (non-bonded region) between the substrate and the pressure-sensitive adhesive may occur. In addition, printing may be performed on the side of the pressure-sensitive adhesive layer of the protective film or film for forming a protective film by laser irradiation, but the visibility of printing through the substrate and the pressure-sensitive adhesive layer may decrease depending on the uneven shape of the pressure-sensitive adhesive layer.

Japanese Patent No. 5432853

The present invention is a support sheet comprising a pressure-sensitive adhesive layer on the uneven side of a substrate, and in the composite sheet for forming a protective film having a film for forming a protective film on the pressure-sensitive adhesive layer, good adhesion between the substrate and the pressure-sensitive adhesive, and the formation of a protective film or protective film An object of the present invention is to provide a support sheet capable of realizing good printing visibility through a support sheet for a film, and a composite sheet for forming a protective film provided with the support sheet.

The present invention includes the following aspects.

[1] A support sheet provided with a substrate and provided with a pressure-sensitive adhesive layer on the substrate, wherein the surface on the side of the pressure-sensitive adhesive layer of the substrate is an uneven surface, and a test piece is cut out from five places of the support sheet, and WHEREIN: When the cross section of an adhesive layer is observed, the maximum value (d1) of the interlayer distance between the said base material and said adhesive layer is 0.5 micrometers or less.

[2] The support sheet according to [1], wherein the pressure-sensitive adhesive layer is in direct contact with the uneven surface of the substrate.

[3] When a test piece is cut out from five places of the support sheet, and in these five test pieces, when the cross section of the pressure-sensitive adhesive layer is observed, the number of regions where the substrate and the pressure-sensitive adhesive layer are not bonded is in the test piece. And the support sheet according to [1] or [2], wherein the total number of each test piece is 5 or less when observed from a region of 1 mm in the center of the cross section of the test piece in the width direction.

[4] a step of preparing a first laminated sheet in which a substrate, an adhesive layer, and a first release film are provided in this order, and the surface on the side of the adhesive layer of the substrate is an uneven surface,

The method for producing a support sheet according to any one of [1] to [3], including a step of storing the first laminated sheet at 53 to 75°C for 24 to 720 hours.

[5] A composite sheet for forming a protective film, comprising a film for forming a protective film on the pressure-sensitive adhesive layer in the support sheet according to any one of [1] to [3] above.

[6] A first laminated sheet comprising a substrate, an adhesive layer, and a first release film in this order, wherein the pressure-sensitive adhesive layer side surface of the substrate is an uneven surface, a third release film, a film for forming a protective film, and a second release film The process of preparing a laminated film provided in this order,

A step of storing the first laminated sheet at 53 to 75°C for 24 to 720 hours,

The first release film and the second release film are removed, and the exposed surface of the pressure-sensitive adhesive layer and the exposed surface of the protective film-forming film are bonded to each other, and the substrate, the pressure-sensitive adhesive layer, the protective film-forming film, and the third peeling A process of manufacturing a second laminated sheet having a film in this order, and

The method for producing a composite sheet for forming a protective film according to [5], comprising the step of storing the second laminated sheet at 53 to 75°C for 24 to 720 hours.

[7] The step of bonding the exposed surface of the pressure-sensitive adhesive layer and the exposed surface of the protective film-forming film is performed while pressing at a pressure of 0.3 to 0.8 MPa at 53 to 75°C, forming the protective film according to [6]. Method for producing a composite sheet for use.

[8] The first laminated sheet, the laminated film, and the second laminated sheet are each a long laminated sheet or a laminated film, and the first laminated sheet and the second laminated sheet are each in the storing step , The production method according to [6] or [7], which is wound up in a roll shape and stored.

By constructing the composite sheet for forming a protective film using the support sheet of the present invention, good adhesion between the substrate and the pressure-sensitive adhesive and good printing visibility through the support sheet for the protective film or film for forming a protective film can be realized.

1 is a cross-sectional view schematically showing a supporting sheet and a composite sheet for forming a protective film according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention together with a support sheet.
3 is a cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention together with a support sheet.
4 is an enlarged cross-sectional view of the supporting sheet and the composite sheet for forming a protective film shown in FIG. 1.

◇Composite sheet for supporting sheet and protective film formation

A support sheet according to an embodiment of the present invention is a support sheet having a substrate and a pressure-sensitive adhesive layer on the substrate, wherein the pressure-sensitive adhesive layer side surface of the substrate is an uneven surface, and a test piece is removed from five locations of the support sheet. Cut out and observe the cross section of the pressure-sensitive adhesive layer in these five test pieces, the maximum value of the interlayer distance between the substrate and the pressure-sensitive adhesive layer (in this specification, it may be referred to as "d1") is 0.5 μm Below.

Since the maximum value d1 of the interlayer distance between the substrate and the pressure-sensitive adhesive layer is 0.5 μm or less, good adhesion between the substrate and the pressure-sensitive adhesive and good print visibility through a support sheet of a protective film or a film for forming a protective film can be realized.

A support sheet according to an embodiment of the present invention is a support sheet having a substrate and a pressure-sensitive adhesive layer on the substrate, wherein the pressure-sensitive adhesive layer side surface of the substrate is an uneven surface, and a test piece is removed from five locations of the support sheet. Cut out, and in these five test pieces, when the minimum and maximum values of the thickness of the pressure-sensitive adhesive layer were obtained, respectively, the average value of the minimum values (in this specification, it may be referred to as “S value”) becomes 1.5 μm or more. , It is preferable that the average value of the maximum value (in this specification, it may be referred to as “L value”) is 9 μm or less.

Further, it is preferable that the number of unbonded regions between the substrate and the pressure-sensitive adhesive layer is 5 or less when a test piece is cut out from five locations of the support sheet, and the cross section of the pressure-sensitive adhesive layer is observed in these five test pieces. Do.

Further, the composite sheet for forming a protective film according to an embodiment of the present invention includes a film for forming a protective film on the pressure-sensitive adhesive layer in the support sheet.

Further, since the S value of the pressure-sensitive adhesive layer is 1.5 μm or more, the lamination property of the pressure-sensitive adhesive layer and the film for forming a protective film tends to be good. In the present specification, "lamination" means the normality of the stacked state of two layers of interest, unless otherwise noted. "Good lamination" means, for example, that there is no non-bonding region (a void) between two adjacent layers to be targeted, or the number of non-bonded regions is small, and the interlayer distance of the non-bonded region is small. Means that.

On the other hand, since the L value of the pressure-sensitive adhesive layer is 9 μm or less, the printing visibility through the supporting sheet of the protective film or film for forming a protective film is likely to be improved.

The test piece was cut out from five locations of the support sheet, and was obtained by cutting the support sheet over the entire thickness direction. The test piece is a small piece with the entire layer constituting the support sheet.

The size of the test piece is not particularly limited, but the length of one side of the laminated or exposed surface of each layer (substrate, adhesive layer, etc.) constituting the test piece is preferably 2 mm or more. By using a test piece of this size, the S value and L value of the pressure-sensitive adhesive layer are more accurately determined.

The maximum value of the length of one side is not particularly limited. For example, it is preferable that the length of one side is 10 mm or less from the viewpoint of easier preparation of the test piece.

The planar shape of the test piece, that is, the shape of the laminated surface or the exposed surface of each layer (substrate, pressure-sensitive adhesive layer, etc.) constituting the test piece is preferably a polygonal shape, and a square shape is more convenient to cut the test piece. More preferable.

As a preferable test piece, for example, a laminated surface or an exposed surface of each layer (substrate, pressure-sensitive adhesive layer, etc.) constituting the test piece may have a square shape having a size of 3 mm×3 mm. However, this is an example of a preferred test piece.

The position at which the five specimens are cut out in the support sheet is not particularly limited, but may be selected in consideration of the position to be laminated of the film for forming a protective film to be described later so that the S value and L value of the pressure-sensitive adhesive layer can be more accurately determined. .

For example, one of the positions where the protective film-forming film is to be stacked on the support sheet, the center (weight center) of the protective film-forming film is scheduled to be disposed, and a part near the periphery of the protective film-forming film. About the center (center of weight) part, the position of the point object is roughly mentioned, 4 places and 5 places which are planned to arrange|position.

In the support sheet, it is preferable that the distance between the centers (centers of weight) at the cut-out positions of the test pieces is 50 to 200 mm. By doing in this way, the S value and the L value of an adhesive layer can be calculated|required more precisely.

In order to obtain the S value and L value of the pressure-sensitive adhesive layer from the test piece, a cross-section is newly formed in the test piece, and in the formed cross-section, the minimum and maximum values of the thickness of the pressure-sensitive adhesive layer can be measured for each test piece.

The newly formed cross section per test piece may be only one or two or more, but usually only one is sufficient.

In addition, the S value and the L value can be calculated from these at least five minimum and maximum values.

In the test piece, a cross section can be formed by a known method. For example, by using a known cross-section sample preparation device (cross section polisher), it is possible to form a cross section in a test piece with high reproducibility by suppressing variation.

The minimum and maximum values of the thickness of the pressure-sensitive adhesive layer can be measured, for example, by observing the cross section of the test piece using a scanning electron microscope (SEM).

In the cross section of each test piece, the region in which the maximum value (d1) of the interlayer distance between the substrate and the pressure-sensitive adhesive layer is measured is a direction perpendicular to the lamination direction of each layer (substrate, pressure-sensitive adhesive layer, etc.) constituting the test piece ( It is preferable that it is a region of 50 to 1500 µm in a direction substantially parallel to the laminated surface or the exposed surface of each layer). By doing in this way, it is possible to measure the maximum value (d1) of the interlayer distance between the base material and the pressure-sensitive adhesive layer with high efficiency and high precision. The measurement of the minimum and maximum values of the thickness of the pressure-sensitive adhesive layer is also the same.

When the minimum values of the thickness of the pressure-sensitive adhesive layer are compared between the support sheet at the stage where the composite sheet for forming a protective film is not formed and the support sheet constituting the composite sheet for forming a protective film, these minimum values are the same as each other, or The minimum value in the support sheet constituting the composite sheet for forming a protective film is a degree to be slightly smaller, and even when such a decrease is made, the difference is negligible.

The same applies to the maximum value of the thickness of the pressure-sensitive adhesive layer. That is, when the maximum value of the thickness of the pressure-sensitive adhesive layer is compared between the support sheet at the stage where the protective film-forming composite sheet is not formed and the support sheet constituting the protective film-forming composite sheet, these maximum values are the same. Alternatively, the maximum value in the support sheet constituting the composite sheet for forming a protective film is a degree to be slightly smaller, and even when such a decrease is made, the difference is negligible.

Therefore, the maximum value (d1) of the interlayer distance may be obtained in the same manner as in the case of using the test piece cut out from the support sheet using the test piece cut from the composite sheet for forming a protective film instead of the support sheet, and the S value and the L value of the adhesive layer You can get When the test piece cut out from the composite sheet for forming a protective film as described above is used, when the maximum value d1 of the interlayer distance is 0.5 μm or less, the composite sheet for forming a protective film reflects the effects of the present invention described above.

That is, the composite sheet for forming a protective film according to an embodiment of the present invention is a composite sheet for forming a protective film having a film for forming a protective film on the pressure-sensitive adhesive layer in the support sheet, and test pieces are taken from five locations of the composite sheet for forming a protective film. When cut out and the cross section of the pressure-sensitive adhesive layer is observed in these five test pieces, the maximum value d1 of the interlayer distance between the substrate and the pressure-sensitive adhesive layer is 0.5 μm or less.

Similarly, in the same manner as in the case where the test piece cut from the support sheet was used instead of the support sheet at the stage where the protective film-forming composite sheet was not formed, the pressure-sensitive adhesive layer S Value and L value may be obtained. When a test piece cut out from the composite sheet for forming a protective film is used as described above, when the S value of the pressure-sensitive adhesive layer is 1.5 μm or more and the L value of the pressure-sensitive adhesive layer is 9 μm or less, the composite sheet for forming a protective film is It is easy to reflect the effects of the invention.

That is, the composite sheet for forming a protective film according to an embodiment of the present invention is a composite sheet for forming a protective film having a film for forming a protective film on the pressure-sensitive adhesive layer in the support sheet, and test pieces are taken from five locations of the composite sheet for forming a protective film. Cut out and in these five test pieces, when the minimum and maximum values of the thickness of the pressure-sensitive adhesive layer were obtained, respectively, the average value (S value) of the minimum values became 1.5 μm or more, and the average value (L value) of the maximum values was 9 It is preferable to be less than or equal to µm.

On the other hand, the test piece cut out from the composite sheet for forming a protective film is obtained by cutting the composite sheet for forming a protective film over the entire thickness direction, and is a small piece provided with the entire layer constituting the composite sheet for forming a protective film.

Hereinafter, the overall configuration of the composite sheet for forming a protective film of the present invention will be described with reference to the drawings. Meanwhile, in the drawings used in the following description, for convenience, in order to make it easier to understand the features of the present invention, the main part may be enlarged and shown, and the dimensional ratio of each component is not limited to the same as in reality. .

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

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

In the composite sheet 1A for forming a protective film, a pressure-sensitive adhesive layer 12 is laminated on one side of the substrate 11 (in this specification, it may be referred to as a “first side”) 11a, and the pressure-sensitive adhesive layer A protective film-forming film 13 is laminated on the entire surface of 12a on the side opposite to the substrate 11 side in (12) (in this specification, it may be referred to as ``first surface'') A jig adhesive layer on a part of the surface of the film 13 on the opposite side to the pressure-sensitive adhesive layer 12 side (in this specification, it may be referred to as a ``first surface'') 13a, that is, a region near the periphery (16) is laminated and, of the first surface 13a of the protective film forming film 13, the surface on which the jig adhesive layer 16 is not laminated, and the protective film forming film of the jig adhesive layer 16 The release film 15 is laminated on the surface 16a (upper surface and side surface) not in contact with (13).

In addition, in FIG. 1, reference numeral 13b denotes a surface on the side of the pressure-sensitive adhesive layer 12 of the film 13 for forming a protective film (in this specification, it may be referred to as a "second surface").

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

In the composite sheet 1A for forming a protective film, the first surface 11a of the substrate 11 is an uneven surface.

Further, the pressure-sensitive adhesive layer 12 is formed in direct contact with the first surface (corrugated surface) 11a of the substrate 11. For this reason, the surface on the side of the substrate 11 of the pressure-sensitive adhesive layer 12 (in this specification, it may be referred to as a "second surface") 12b is an uneven surface.

In the composite sheet 1A for forming a protective film, the side opposite to the side of the pressure-sensitive adhesive layer 12 of the substrate 11 (in this specification, it may be referred to as a ``second side'') 11b is an uneven surface and Any one of a smooth surface (non-convex and convex surface) may be used, but a smooth surface is preferable. The second side 11b of the substrate 11 is a side opposite to the side of the protective film-forming film 13 of the support sheet 10 (in this specification, it may be referred to as a ``second side'') (10b) This can also be said.

The "uneven surface" and the "smooth surface" will be described in detail next.

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

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

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

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

Also in the composite sheet 1B for forming a protective film, the first surface 11a of the substrate 11 is an uneven surface.

Further, the pressure-sensitive adhesive layer 12 is formed in direct contact with the first surface (corrugated surface) 11a of the substrate 11. For this reason, the surface (2nd surface) 12b of the base material 11 side of the adhesive layer 12 is an uneven surface.

Also in the composite sheet 1B for forming a protective film, the second surface 11b of the substrate 11 (that is, the second surface 10b of the support sheet 10) is formed of an uneven surface and a smooth surface (non-corrugated surface). Any one may be sufficient, but it is preferable that it is a smooth surface.

The protective film-forming composite sheet 1B shown in FIG. 2 is provided with a semiconductor wafer in a part of the center side of the first surface 13a of the protective film-forming film 13 with the release film 15 removed. The rear surface of (not shown) is affixed, and a region near the periphery is affixed to a jig such as a ring frame and used.

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

The protective film-forming composite sheet 1C shown here is the same as the protective film-forming composite sheet 1B shown in FIG. 2 except that the shape of the protective film-forming film is different. That is, the protective film-forming composite sheet 1C includes a substrate 11, an adhesive layer 12 on the substrate 11, and a protective film forming film 23 on the adhesive layer 12. Are doing. The support sheet 10 is a laminate of the substrate 11 and the pressure-sensitive adhesive layer 12, and the protective film-forming composite sheet 1C is, in other words, the first side of the support sheet 10 (the protective film-forming film 23). It has a configuration in which the film 23 for forming a protective film is laminated on the side surface) (10a). In addition, the protective film-forming composite sheet 1C is further provided with a release film 15 on the protective film-forming film 23.

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

In addition, in FIG. 3, reference numeral 23b denotes a surface on the side of the pressure-sensitive adhesive layer 12 of the film 23 for forming a protective film (in this specification, it may be referred to as a "second surface").

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

Also in the composite sheet 1C for forming a protective film, the first surface 11a of the substrate 11 is an uneven surface.

Further, the pressure-sensitive adhesive layer 12 is formed in direct contact with the first surface (corrugated surface) 11a of the substrate 11. For this reason, the surface (2nd surface) 12b of the base material 11 side of the adhesive layer 12 is an uneven surface.

Also in the composite sheet 1C for forming a protective film, the second surface 11b of the base material 11 (that is, the second surface 10b of the support sheet 10) is formed of an uneven surface and a smooth surface (non-corrugated surface). Any one may be sufficient, but it is preferable that it is a smooth surface.

In the protective film-forming composite sheet 1C shown in FIG. 3, the back surface of a semiconductor wafer (not shown) is affixed to the surface 23a of the protective film-forming film 23 in the state in which the release film 15 is removed, Of the first surface 12a of the pressure-sensitive adhesive layer 12, a region in which the protective film-forming film 23 is not laminated is affixed to a jig such as a ring frame and used.

On the other hand, in the composite sheet 1C for forming a protective film shown in FIG. 3, in the region of the first surface 12a of the pressure-sensitive adhesive layer 12, in a region in which the protective film forming film 23 is not laminated, as shown in FIG. Similarly, the jig adhesive layer may be laminated (not shown). In the composite sheet 1C for forming a protective film having such a jig adhesive layer, the upper surface of the jig adhesive layer is affixed to a jig such as a ring frame in the same manner as the composite sheet for forming a protective film shown in FIG. 1 and used.

As described above, the composite sheet for forming a protective film may have any form of the supporting sheet and the film for forming a protective film, or may be provided with an adhesive layer for a jig. However, usually as shown in FIG. 1, as a composite sheet for forming a protective film having a jig adhesive layer, it is preferable that a jig adhesive layer is provided on a film for forming a protective film.

The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to those shown in Figs. 1 to 3, and within a range that does not impair the effects of the present invention, some configurations of those shown in Figs. It may be changed or deleted, or another configuration may be added to the one described so far.

For example, in the composite sheet for forming a protective film shown in FIGS. 1 to 3, an intermediate layer may be formed between the substrate 11 and the pressure-sensitive adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be constituted by laminating a substrate, an intermediate layer, and an adhesive layer in this order in their thickness direction. Any intermediate layer may be selected according to the purpose.

In addition, in the composite sheet for forming a protective film shown in Figs. 1 to 3, layers other than the intermediate layer may be formed at arbitrary locations.

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

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

However, as shown in Figs. 1 to 3, in the composite sheet for forming a protective film, the pressure-sensitive adhesive layer is in direct contact with the uneven surface (first surface) of the substrate, that is, an intermediate layer is formed between the substrate and the pressure-sensitive adhesive layer. It is not provided, and it is preferable that the pressure-sensitive adhesive layer is directly contacted and laminated on the substrate.

In addition, in the protective film-forming composite sheet, the protective film-forming film is in direct contact with the first surface of the pressure-sensitive adhesive layer, that is, no other layer is provided between the pressure-sensitive adhesive layer and the protective film-forming film, and the pressure-sensitive adhesive layer It is preferable that the protective film-forming film is directly contacted and laminated thereon.

In addition, the protective film-forming composite sheet satisfies these conditions together, i.e., the substrate, the pressure-sensitive adhesive layer, and the protective film-forming film are laminated in direct contact with each other in this order in their thickness direction, so that it is more desirable.

It is preferable that the support sheet is transparent.

The supporting sheet may be colored depending on the purpose, or other layers may be deposited.

For example, when the film for forming a protective film is energy ray-curable, it is preferable that the supporting sheet transmit energy rays.

In the present specification, the term "energy rays" means having both energy among electromagnetic waves or charged particle rays, and examples thereof include ultraviolet rays, radiation, and electron rays. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet source. The electron beam can be irradiated with what is generated by an electron beam accelerator or the like.

In the present specification, "energy ray curable" means a property that is hardened by irradiation with energy rays, and "non-energy ray curable property" means a property that is not cured even when irradiated with energy rays.

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

In the support sheet, the upper limit of the transmittance of light having a wavelength of 375 nm is not particularly limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is within such a range, when a film for forming a protective film or a protective film is irradiated with laser light through a support sheet and printed on them, printing can be performed more clearly.

In the support sheet, the upper limit of the transmittance of light having a wavelength of 532 nm is not particularly limited. For example, the transmittance of the light may be 95% or less.

In the support sheet, the transmittance of light having a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is within such a range, when a film for forming a protective film or a protective film is irradiated with laser light through a support sheet and printed on them, printing can be performed more clearly.

In the support sheet, the upper limit of the transmittance of light having a wavelength of 1064 nm is not particularly limited. For example, the transmittance of the light may be 95% or less.

The transmission clarity of the supporting sheet is preferably 30 or more, more preferably 100 or more, and particularly preferably 200 or more. When the transmittance clarity is within such a range, it becomes easier to confirm the lifting and peeling of the film for forming a protective film, problems of printing, and defects through the support sheet.

The transmission sharpness of the support sheet is not particularly limited. For example, the transmission sharpness may be 430 or less.

The transmission sharpness of the support sheet can be measured in accordance with JIS K 7374-2007.

Next, each layer constituting the supporting sheet and the composite sheet for forming a protective film will be described in detail.

○ Description

The substrate is in the form of a sheet or a film, and has an uneven surface.

In the present specification, the "uneven surface" means a surface having a maximum height roughness Rz of 0.01 µm or more specified in JIS B 0601:2013.

In addition, the "smooth surface" is not an uneven surface, but means a surface with high smoothness, and is also referred to as a "non-corrugated surface" or a "glossy surface". For example, the smooth surface includes a surface with an extremely small irregularity that does not correspond to the irregularity surface.

In the base material, only one surface may be an uneven surface, and both surfaces may be both an uneven surface, but it is preferable that only one surface is an uneven surface. In other words, in the substrate, it is preferable that only one surface is a smooth surface. In the support sheet, the uneven surface of the base material becomes the side surface provided with the pressure-sensitive adhesive layer.

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

When the substrate is made of a plurality of layers, the surface of the outermost layer (the surface closest to the adhesive layer, or both surfaces of the surface closest to and farthest to the adhesive layer) among these plurality of layers becomes the uneven surface.

In the present specification, it is not limited to the case of the description, and "the multiple layers may be the same or different from each other" means "all the layers may be the same, all layers may be different, and only some of the layers may be the same". It means that "the multiple layers are different from each other" means "at least one of the constituent materials and thicknesses of each layer are different from each other".

In the uneven surface (first surface) of the side with the pressure-sensitive adhesive layer of the substrate, the maximum height roughness (Rz) measured in accordance with JIS B 0601:2013 is preferably 0.01 to 8 µm, and 0.1 to 7 µm. It is more preferable and it is especially preferable that it is 0.5-6 micrometers. Since the Rz of the base material is equal to or greater than the lower limit, the occurrence of problems when the base material is individually wound up in a roll shape and unwound is suppressed. Further, in the manufacturing process of the supporting sheet or the composite sheet for forming a protective film, similarly to a laminate including a substrate, the occurrence of a problem when winding and unwinding is suppressed. On the other hand, since the Rz of the base material is equal to or less than the above upper limit, both the lamination property of the pressure-sensitive adhesive layer and the film for forming a protective film, and the print visibility through the supporting sheet of the protective film or the film for forming a protective film become good.

When both surfaces of the substrate are uneven, the unevenness of both surfaces may be the same or different.

As a constituent material of the said base material, various resins are mentioned, for example.

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

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

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

In this specification, "(meth)acrylic acid" shall be 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 number of resins constituting the base material may be only one type, or may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

The thickness of the substrate is preferably in the range of 50 to 300 µm, and more preferably in the range of 60 to 150 µm. When the thickness of the substrate is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to the semiconductor wafer or semiconductor chip are further improved.

As described above, since the substrate has an uneven surface, its thickness varies depending on the portion of the substrate. Therefore, the minimum value of the base material thickness may be equal to or greater than the lower limit value, and the maximum value of the base material thickness may be equal to or less than the upper limit value.

On the other hand, "substrate thickness" means the thickness of the entire substrate, and, for example, the substrate thickness composed of a plurality of layers means the total thickness of all layers constituting the substrate.

The substrate thickness can be measured, for example, by observing the side or cross section of the substrate using a scanning electron microscope (SEM).

The cross-section of the base material can be formed by the same method as in the case of the cross-section in the test piece of the support sheet and the composite sheet for forming a protective film, for example.

For example, in the same manner as described above, a test piece is cut out from a plurality of locations (e.g., 5 locations) of a supporting sheet or a composite sheet for forming a protective film, and in this test piece, the minimum and maximum values of the substrate thickness are obtained. , When the average value of these minimum values and the average value of the maximum value are calculated from these values, the average value of the minimum value may be equal to or greater than the lower limit of the thickness of the substrate described above, and the average value of the maximum value may be equal to or less than the upper limit of the thickness of the substrate.

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

It is preferable that the substrate is transparent.

The substrate may be colored depending on the purpose, or other layers may be deposited.

For example, when the film for forming a protective film is energy ray-curable, it is preferable that the substrate transmits energy rays.

The substrate is oxidized by corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc. in order to improve the adhesion with the layer in direct contact such as the pressure-sensitive adhesive layer formed thereon. Treatment or the like may be applied to the surface.

In addition, the substrate may have a surface subjected to a primer treatment.

In addition, the base material is an antistatic coating layer; When the composite sheet for forming a protective film is superimposed and stored, it may have a layer that prevents the substrate from adhering to another sheet, or a layer that prevents the substrate from adhering to the adsorption table.

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

When using a base material that does not have an uneven surface (that is, a base material whose both sides are smooth surfaces), the smooth surface of the base material may be subjected to an uneven treatment.

The uneven treatment can be performed by a known method. For example, by using a metal roll or a metal plate having an uneven surface to press the uneven surface against the smooth surface of the base material, the smooth surface of the base material can be subjected to an uneven treatment. At this time, it is preferable to press the heated metal roll or metal plate to the smooth surface of the substrate. Further, the smooth surface of the substrate can be subjected to an uneven treatment by sand blast treatment or solvent treatment.

○Adhesive layer

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

In the pressure-sensitive adhesive layer, usually, regardless of the presence or absence of an intermediate layer between the substrate and the pressure-sensitive adhesive layer, at least the substrate-side surface is an uneven surface under the influence of the uneven surface of the substrate.

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

When the pressure-sensitive adhesive layer is made of a plurality of layers, the surface of the outermost layer (the surface closest to the base material) among the plurality of layers becomes the uneven surface.

Here, the substrate and the pressure-sensitive adhesive layer will be described in more detail with reference to the drawings.

4 is an enlarged cross-sectional view schematically showing a composite sheet for forming a protective film according to an embodiment of the present invention. Here, the composite sheet 1A for forming a protective film shown in Fig. 1 will be described as an example. In addition, in FIG. 4, illustration of a release film is abbreviate|omitted.

As described above, the first surface 11a of the substrate 11 is an uneven surface. In addition, the pressure-sensitive adhesive layer 12 is formed in direct contact with the first surface (uneven surface) 11a of the substrate 11, and the second surface 12b of the pressure-sensitive adhesive layer 12 is made of the substrate 11 It becomes easy to follow one surface 11a. Accordingly, the second surface 12b of the pressure-sensitive adhesive layer 12 also becomes an uneven surface.

The thickness T _a of the pressure-sensitive adhesive layer 12 is not constant and fluctuates depending on the portion of the pressure-sensitive adhesive layer 12. Here, the minimum value of the thickness of the pressure-sensitive adhesive layer 12 is indicated by the symbol T _a1 , and the maximum value of the thickness of the pressure-sensitive adhesive layer 12 is indicated by the symbol T _a2 .

In the composite sheet 1A for forming a protective film, a test piece is cut out from the five places, and a cross section is formed in these five test pieces, and in this newly formed cross section, the minimum value T _a1 and the maximum of the thickness of the pressure-sensitive adhesive layer, respectively. The value T _a2 is obtained. And, when the average value (the S value) is calculated from at least five T _a1 values, it is preferably 1.5 μm or more, and when the average value (the L value) is calculated from at least five T _a2 values, 9 It is preferable to be less than or equal to μm.

Cut-out of the test piece from the composite sheet for forming a protective film (1A), formation of a cross-section in the test piece, measurement of the maximum value (d1) of the interlayer distance between the substrate and the pressure-sensitive adhesive layer in the cross-section, and the adhesive layer The measurement of the minimum value T _a1 and the maximum value T _a2 of the thickness of can be performed in the same manner as when the test piece is cut out from the supporting sheet not including the composite sheet for forming a protective film as described above.

On the other hand, the enlarged cross-sectional view of the support sheet not constituting the composite sheet for forming a protective film is the same as that omitting the illustration of the film 13 for forming a protective film in FIG. 4.

As the composite sheet 1A for forming a protective film, a region between the substrate 11 and the pressure-sensitive adhesive layer 12 in which they are not bonded (in this specification, it may be referred to as a “non-bonded region”) 91 Indicates that there is. However, even if the protective film-forming composite sheet 1A has such a non-bonded region 91, the size of the non-bonded region 91 in the thickness direction of the protective film-forming composite sheet 1A, that is, the substrate and the adhesive The protective film-forming composite sheet 1A having a maximum value (d1) of the interlayer distance between the layers of 0.5 μm or less has good adhesion between the substrate 11 and the pressure-sensitive adhesive layer 12, and a support sheet for a protective film or film for forming a protective film is interposed therebetween. As long as it has good print visibility.

In addition, in this specification, "the size of the non-bonded area in the thickness direction of the composite sheet for protective film formation" means "the interlayer distance in the thickness direction of the said sheet of two adjacent layers in the composite sheet for protective film formation" ", and may be simply referred to as "the distance between floors". For example, the "size of the non-bonded region 91 in the thickness direction of the protective film-forming composite sheet 1A" means "the substrate 11 and the adhesive in the thickness direction of the sheet 1A. It means the interlayer distance between the layers 12".

When the size (interlayer distance) of one non-bonded area fluctuates, the maximum value is adopted as the size (interlayer distance) of the non-bonded area.

The size (interlayer distance) of the non-bonding region can be measured in the same manner as in the case of the maximum value (d1) of the interlayer distance between the substrate and the pressure-sensitive adhesive layer described above. That is, a cross section is formed in the test piece of the composite sheet for forming a protective film by the same method as when the R value of the pressure-sensitive adhesive layer is determined, and the size of the non-bonded region in this cross section can be determined. Alternatively, without producing a test piece, a cross section may be formed from the composite sheet for forming a protective film itself, and the size of the non-bonded region may be determined in this cross section.

The size of the non-bonded region 91 (the maximum value of the interlayer distance) may be any one of 0.4 µm or less, 0.3 µm or less, 0.2 µm or less, and 0.1 µm or less, for example.

In the composite sheet 1A for forming a protective film, the non-bonded region 91 may not exist at all. In the present specification, when the size of the non-bonded region is 0.05 μm or more, it is recognized that the non-bonded region exists, but when the non-bonded region 91 does not exist at all, the size of the non-bonded region 91 (interlayer distance ) Is sometimes expressed as 0㎛.

Here, the base material and the pressure-sensitive adhesive layer have been described with the composite sheet 1A for forming a protective film, for example, but forming a protective film in other embodiments such as the composite sheet 1B for forming a protective film and the composite sheet 1C for forming a protective film. In the case of the composite sheet for use, the base material and the pressure-sensitive adhesive layer are the same.

The S value of the pressure-sensitive adhesive layer is not particularly limited as long as the effect of the present invention is not impaired, but it is preferably 1.5 μm or more and less than 9 μm. It is more preferably 1.7 µm or more, particularly preferably 1.9 µm or more, and for example, any one of 2.3 µm or more, 2.7 µm or more, 3.1 µm or more, and 3.5 µm or more may be used. Since the S value is not less than the lower limit, the lamination property of the pressure-sensitive adhesive layer and the film for forming a protective film becomes better.

On the other hand, the S value of the pressure-sensitive adhesive layer may be 8 μm or less, for example. Such an adhesive layer can be formed more easily.

The S value of the pressure-sensitive adhesive layer can be appropriately adjusted within a range set by arbitrarily combining the above-described preferred lower and upper limits. For example, the S value of the pressure-sensitive adhesive layer is preferably 1.5 to 8 μm, more preferably 1.7 to 8 μm, still more preferably 1.9 to 8 μm, for example, 2.3 to 8 μm, 2.7 to 8 μm. , 3.1 to 8 µm, and 3.5 to 8 µm may be used. However, these are examples of the S value of the pressure-sensitive adhesive layer.

The L value of the pressure-sensitive adhesive layer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 9 μm or less, and is preferably larger than 1.5 μm. It is more preferable that it is 8.6 micrometers or less, and it is especially preferable that it is 8.3 micrometers or less, For example, any one of 7.7 micrometers or less, 7.3 micrometers or less, 6.9 micrometers or less, and 6.5 micrometers or less may be sufficient. Since the L value is less than or equal to the above upper limit, the printing visibility through the support sheet of the protective film or the film for forming a protective film becomes better.

On the other hand, the L value of the pressure-sensitive adhesive layer may be, for example, 2.5 μm or more. Such an adhesive layer can be formed more easily.

The L value of the pressure-sensitive adhesive layer can be appropriately adjusted within a range set by arbitrarily combining the above-described preferred lower and upper limits. For example, the L value of the pressure-sensitive adhesive layer is preferably 2.5 to 9 µm, more preferably 2.5 to 8.6 µm, still more preferably 2.5 to 8.3 µm, for example, 2.5 to 7.7 µm, 2.5 to 7.3 µm. , 2.5 to 6.9 µm, and 2.5 to 6.5 µm may be used.

The thickness of the pressure-sensitive adhesive layer (for example, T _a ) is not particularly limited as long as it does not impair the effect of the present invention, but it is preferable to satisfy the conditions of the S value and L value described above.

For example, the thickness of the pressure-sensitive adhesive layer may be 1.5 to 9 µm.

On the other hand, the "thickness of the adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers means the total thickness of all layers constituting the pressure-sensitive adhesive layer. From this point of view, the minimum and maximum values of the thickness of the pressure-sensitive adhesive layer described above are defined.

The adhesive layer contains an adhesive.

Examples of the pressure-sensitive adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ether, polycarbonate, and ester resins, and acrylic resins are preferable.

In the present specification, "adhesive resin" is a concept including both a resin having adhesiveness and a resin having adhesiveness, for example, not only the resin itself has adhesiveness, but also used in combination with other components such as additives It also includes a resin that exhibits adhesiveness by means of, and a resin that exhibits adhesiveness by the presence of a trigger such as heat or water.

It is preferable that the pressure-sensitive adhesive layer is transparent.

The pressure-sensitive adhesive layer may be colored depending on the purpose.

For example, when the film for forming a protective film is energy ray-curable, it is preferable that the pressure-sensitive adhesive layer transmits energy rays.

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

<<adhesive composition>>

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, by coating the pressure-sensitive adhesive composition on the surface to be formed of the pressure-sensitive adhesive layer and drying as necessary, the pressure-sensitive adhesive layer can be formed on a target site. A more specific method of forming the pressure-sensitive adhesive layer will be described in detail next, along with methods of forming other layers. In the pressure-sensitive adhesive composition, the content ratio between components that do not vaporize at room temperature is usually the same as the content ratio between the components in the pressure-sensitive adhesive layer.

In the present specification, "room temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25°C.

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

Drying conditions of the pressure-sensitive adhesive composition are not particularly limited, but when the pressure-sensitive adhesive composition contains a solvent to be described later, it is preferable to heat-dry. It is preferable to dry the pressure-sensitive adhesive composition containing a solvent under the conditions of 10 seconds to 5 minutes at 70-130 degreeC, for example.

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, includes, for example, a non-energy-ray-curable pressure-sensitive adhesive resin (I-1a) (hereinafter referred to as ``adhesive resin ( I-1a)") and an energy ray-curable compound (I-1); Containing an energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) (hereinafter, it may be abbreviated as ``adhesive resin (I-2a)'') Pressure-sensitive adhesive composition (I-2); The adhesive composition (I-3) containing the said adhesive resin (I-2a) and an energy ray-curable compound, etc. are mentioned.

<Adhesive composition (I-1)>

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

[Adhesive resin (I-1a)]

It is preferable that the said adhesive resin (I-1a) is an acrylic resin.

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

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

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

More specifically as (meth)acrylate alkyl ester, (meth) acrylate methyl, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) Isobutyl acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth) Isooctyl acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate ((meth) ) Lauryl acrylate), (meth) tridecyl acrylate, (meth) tetradecyl acrylate ((meth) myristyl acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate ((meth) palmityl acrylate), Heptadecyl (meth)acrylate, octadecyl (meth)acrylate ((meth) acrylate stearyl), 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 an alkyl (meth)acrylate having 4 or more carbon atoms in the alkyl group. And since the adhesive force of the pressure-sensitive adhesive layer is further improved, the alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Further, the alkyl group having 4 or more carbon atoms is preferably an alkyl acrylate ester.

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

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

Among the functional group-containing monomers, examples of the functional group include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group.

That is, as a functional group-containing monomer, a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, etc. are mentioned, for example.

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

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

As for the functional group-containing monomer, a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.

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

In the above acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and 3 to 27% by mass with respect to the total mass of the structural unit. It is particularly preferred.

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

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

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

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

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

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

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

In the pressure-sensitive adhesive composition (I-1), the content of the pressure-sensitive adhesive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass Do.

[Energy ray curable compound]

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

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

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

Since the energy ray-curable compound has a relatively large molecular weight and it is difficult to lower the storage modulus of the pressure-sensitive adhesive layer, urethane (meth)acrylate and urethane (meth)acrylate oligomers are preferable.

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

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

[Crosslinking agent]

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

The crosslinking agent crosslinks the adhesive resins (I-1a) by reacting with the functional group, for example.

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

The crosslinking agent is preferably an isocyanate crosslinking agent from the viewpoint of improving the cohesiveness of the pressure-sensitive adhesive to improve the adhesion of the pressure-sensitive adhesive layer and being easily available.

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

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

[Photopolymerization initiator]

The pressure-sensitive adhesive composition (I-1) may further contain a photoinitiator. Even when the pressure-sensitive adhesive composition (I-1) containing a photoinitiator is irradiated with relatively low energy energy rays such as ultraviolet rays, the curing reaction sufficiently proceeds.

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

Further, examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; A photosensitizer such as amine can also be used.

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

In the pressure-sensitive adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass based on 100 parts by mass of the energy ray-curable compound. It is particularly preferred to be denied.

[Other additives]

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

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

On the other hand, the reaction retarding agent suppresses the progress of an undesired crosslinking reaction in the pressure-sensitive adhesive composition (I-1) during storage due to the action of a catalyst incorporated in the pressure-sensitive adhesive composition (I-1), for example. . Examples of the reaction retarding agent include forming a chelate complex by chelate to a catalyst, and more specifically, one having two or more carbonyl groups (-C(=O)-) in one molecule. .

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

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

[menstruum]

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

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

As the solvent, for example, the one used in the production of the adhesive resin (I-1a) may be used as it is in the adhesive composition (I-1) without removing from the adhesive resin (I-1a), or the adhesive resin ( A solvent of the same or different type as used in the production of I-1a) may be added separately during the production of the pressure-sensitive adhesive composition (I-1).

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

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

<Adhesive composition (I-2)>

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

[Adhesive resin (I-2a)]

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

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

Examples of the energy ray-polymerizable unsaturated group include (meth)acryloyl group, vinyl group (also referred to as ethenyl group), allyl group (also referred to as 2-propenyl group), and the like, and (meth)acryloyl group Is preferred.

In the adhesive resin (I-1a), as a group capable of bonding with a functional group, an isocyanate group and a glycidyl group capable of bonding with a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding with a carboxy group or an epoxy group, and the like may be mentioned.

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

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

In the pressure-sensitive adhesive composition (I-2), the content of the pressure-sensitive adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass with respect to the total mass of the pressure-sensitive adhesive composition (I-2). It is preferable, and it is especially preferable that it is 10 to 90 mass %.

[Crosslinking agent]

In the case of using the acrylic polymer having structural units derived from monomers containing the same functional group as those in the adhesive resin (I-1a), for example, the adhesive composition (I-2) is added It may contain a cross-linking agent.

Examples of the crosslinking agent in the pressure-sensitive adhesive composition (I-2) include those similar to the crosslinking agent in the pressure-sensitive adhesive composition (I-1).

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

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

[Photopolymerization initiator]

The pressure-sensitive adhesive composition (I-2) may further contain a photoinitiator. Even when the pressure-sensitive adhesive composition (I-2) containing a photoinitiator is irradiated with relatively low energy energy rays such as ultraviolet rays, the curing reaction sufficiently proceeds.

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include those similar to the photopolymerization initiator in the pressure-sensitive adhesive composition (I-1).

The photoinitiators contained in the pressure-sensitive adhesive composition (I-2) may be one type or two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

[Other additives]

The pressure-sensitive adhesive composition (I-2) may contain other additives which do not correspond to any of the above-described components within a range that does not impair the effects of the present invention.

Examples of the other additives in the pressure-sensitive adhesive composition (I-2) include those similar to the other additives in the pressure-sensitive adhesive composition (I-1).

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

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

[menstruum]

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

Examples of the solvent in the pressure-sensitive adhesive composition (I-2) include those similar to the solvent in the pressure-sensitive adhesive composition (I-1).

The number of solvents contained in the pressure-sensitive adhesive composition (I-2) may be only one type, or may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

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

<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) is preferably 5 to 99 mass%, more preferably 10 to 95 mass% with respect to the total mass of the pressure sensitive adhesive composition (I-3). It is preferable, and it is particularly preferable that it is 15 to 90 mass %.

[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, and the pressure-sensitive adhesive composition (I-1) contains The same thing as the energy ray-curable compound is mentioned.

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

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

[Photopolymerization initiator]

The pressure-sensitive adhesive composition (I-3) may further contain a photoinitiator. Even when the pressure-sensitive adhesive composition (I-3) containing a photopolymerization initiator is irradiated with relatively low energy energy rays such as ultraviolet rays, the curing reaction sufficiently proceeds.

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

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

In the adhesive composition (I-3), the content of the photoinitiator is preferably 0.01 to 20 parts by mass, and 0.03 to 10 parts by mass based on 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound. It is more preferable, and it is especially preferable that it is 0.05-5 mass parts.

[Other additives]

The pressure-sensitive adhesive composition (I-3) may contain other additives which do not correspond to any of the above-described components within a range that does not impair the effects of the present invention.

As said other additive, the same thing as the other additive in the adhesive composition (I-1) is mentioned.

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

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

[menstruum]

The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).

Examples of the solvent in the pressure-sensitive adhesive composition (I-3) include those similar to the solvent in the pressure-sensitive adhesive composition (I-1).

The number of solvents contained in the pressure-sensitive adhesive composition (I-3) may be only one, or may be two or more, and in the case of two or more, combinations and ratios thereof can be arbitrarily selected.

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

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

Until now, 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, but what has been described as the components contained therein is an overall pressure-sensitive adhesive composition other than these three pressure-sensitive adhesive compositions. (In this specification, it is referred to as "adhesive composition other than adhesive composition (I-1)-(I-3)"), too.

As the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3), in addition to the energy-ray-curable pressure-sensitive adhesive composition, a non-energy-ray-curable pressure-sensitive adhesive composition is also mentioned.

Examples of the non-energy ray-curable adhesive composition include non-energy ray-curable adhesive resins (I-1a) such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. ) Containing the pressure-sensitive adhesive composition (I-4), preferably containing an acrylic resin.

It is preferable that the pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) contain one or two or more crosslinking agents, and the content is the same as in the case of the pressure-sensitive adhesive composition (I-1) described above. can do.

<Adhesive composition (I-4)>

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

[Adhesive resin (I-1a)]

As the adhesive resin (I-1a) in the adhesive composition (I-4), the same thing as the adhesive resin (I-1a) in the adhesive composition (I-1) can be mentioned.

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

In the pressure-sensitive adhesive composition (I-4), the content of the pressure-sensitive adhesive resin (I-1a) is preferably 5 to 99 mass%, more preferably 10 to 95 mass% with respect to the total mass of the pressure sensitive adhesive composition (I-4). It is preferable, and it is especially preferable that it is 15 to 90 mass %.

In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total content of all components other than the solvent (that is, the content of the pressure-sensitive adhesive resin (I-1a) in the pressure-sensitive adhesive layer) is 30 to 90 It is preferable that it is a mass %, it is more preferable that it is 40 to 85 mass %, It is especially preferable that it is 50 to 80 mass %.

[Crosslinking agent]

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

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

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

In the above pressure-sensitive adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.3 to 50 parts by mass, and more preferably 1 to 100 parts by mass of the content of the adhesive resin (I-1a). It is more preferably 50 parts by mass, and for example, any one of 10 to 50 parts by mass, 15 to 50 parts by mass, and 20 to 50 parts by mass may be used.

[Other additives]

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

As said other additive, the same thing as the other additive in the adhesive composition (I-1) is mentioned.

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

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

[menstruum]

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

Examples of the solvent in the pressure-sensitive adhesive composition (I-4) include those similar to the solvent in the pressure-sensitive adhesive composition (I-1).

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

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

In the composite sheet for forming a protective film, it is preferable that the pressure-sensitive adhesive layer is non-energy ray-curable. This is because, if the pressure-sensitive adhesive layer is energy ray-curable, when curing the protective film-forming film by irradiation with energy rays, the pressure-sensitive adhesive layer may not be cured at the same time. When the pressure-sensitive adhesive layer is cured at the same time as the protective film-forming film, after curing, the protective film-forming film (ie, protective film) and the pressure-sensitive adhesive layer may be affixed to the extent that peeling is impossible at these interfaces. In that case, it becomes difficult to peel the film for forming a protective film after curing, that is, a semiconductor chip having a protective film on the back surface (a semiconductor chip with a protective film) from the support sheet provided with the pressure-sensitive adhesive layer after curing, so that the semiconductor chip with the protective film is normally You will not be able to pick up. In the support sheet, by making the pressure-sensitive adhesive layer non-energy ray curable, such a problem can be reliably avoided, and the semiconductor chip on which the protective film is formed can be picked up more easily.

Here, the effect of the case where the pressure-sensitive adhesive layer is non-energy ray-curable has been described, but even if the layer in direct contact with the protective film-forming film of the support sheet is a layer other than the pressure-sensitive adhesive layer, the same Shows the effect.

<<the manufacturing method of an adhesive composition>>

Pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3), such as pressure-sensitive adhesive compositions (I-1) to (I-3) and pressure-sensitive adhesive compositions (I-4), may be used as the pressure-sensitive adhesive and, if necessary, It is obtained by blending each component for constituting an adhesive composition such as components other than the adhesive.

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

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent, and the compounded component may be diluted beforehand, and the solvent may be mixed with these compounded components without pre-diluting any compounded component other than the solvent. You may use it by doing.

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

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

◎ Film for forming a protective film

The film for forming a protective film becomes a protective film by curing or as it is without curing. This protective film is for protecting the back surface (the side opposite to the electrode formation surface) of the semiconductor wafer or semiconductor chip. The film for forming a protective film is soft and can be easily affixed to the object to be pasted.

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

The film for forming a curable protective film may be either thermosetting or energy ray-curable, or may have properties of both thermosetting and energy ray-curing properties.

The film for protective film formation can be formed using a composition for forming a protective film containing the constituent material.

In the present specification, "non-curable" means a property that is not cured by any means such as heating or irradiation with energy rays.

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

Regardless of the kind, the protective film-forming film may consist of one layer (single layer) or may consist of a plurality of layers of two or more layers. When the film for protective film formation consists of multiple layers, these multiple layers may be the same or different from each other.

Here again, with reference to Figure 4, the pressure-sensitive adhesive layer and the film for forming a protective film will be described in more detail.

As described above, the first surface 11a of the substrate 11 is an uneven surface. However, in the adhesive layer 12, since the S value is, for example, 1.5 μm or more, the influence of the uneven surface is suppressed, and the unevenness in the first surface 12a of the adhesive layer 12 Becomes smaller. For example, even if there exists a region (non-bonded region) 92 between the pressure-sensitive adhesive layer 12 and the protective film-forming film 13, the number of the protective film-forming composite sheet 1A It becomes very few, such as 3 or less over the whole formation area|region of the film 13 for protective film formation. The non-bonded region 92 can be easily confirmed by observing the composite sheet 1A for forming a protective film from the side of the substrate 11, for example.

Further, even if the protective film-forming composite sheet 1A has such a non-bonded region 92, the size of the non-bonded region 92 in the thickness direction of the protective film-forming composite sheet 1A (maximum value of the interlayer distance) The composite sheet 1A for forming a protective film in which) is, for example, 0.5 µm or less has a better lamination property of the pressure-sensitive adhesive layer 12 and the film 13 for forming a protective film. Here, "the size of the non-bonded region 92 (maximum value of the interlayer distance)" means "between the pressure-sensitive adhesive layer 12 and the protective film-forming film 13 in the thickness direction of the protective film-forming composite sheet 1A. It means the maximum value of the interlayer distance of".

The size of the non-bonding region 92 (the maximum value of the interlayer distance) is the same as the maximum value (size) of the interlayer distance of the non-bonding region 91, preferably 0.5 μm or less, for example, Any one of 0.4 µm or less, 0.3 µm or less, 0.2 µm or less, and 0.1 µm or less may be used.

The size of the non-bonding area 92 (maximum value of the interlayer distance) is, for example, the size of the non-bonding area 91 (maximum value of the interlayer distance), except that the combination of the target two layers is different. It can be obtained in the same way as in the case.

In the composite sheet 1A for forming a protective film, the non-bonded region 92 may not exist at all. In the present specification, when the size of the non-bonded region is 0.05 μm or more, it is recognized that the non-bonded region exists, but when the non-bonded region 92 does not exist at all, the size of the non-bonded region 92 (interlayer distance) May be expressed as 0㎛.

On the other hand, as described above, the degree of unevenness on the first surface 12a of the pressure-sensitive adhesive layer 12 tends to be small. For this reason, the thickness T _p of the protective film-forming film 13 is not constant, and fluctuates depending on the portion of the protective film-forming film 13 (adhesive layer 12), but its variation is very small.

In addition, as described above, since the unevenness on the first surface 12a of the pressure-sensitive adhesive layer 12 tends to be small, the pressure-sensitive adhesive layer 12 side surface (the second surface) of the protective film-forming film 13 (13b) is smooth, or the unevenness tends to be small. Therefore, it is difficult to impair the appearance of the protective film-forming film 13.

Further, also in the protective film formed from the protective film-forming film 13, the pressure-sensitive adhesive layer 12 side surface (second surface) is smooth, or the degree of unevenness becomes small, and the appearance of the protective film tends to remain unaffected.

Thus, in the protective film-forming composite sheet 1A, both the protective film-forming film 13 and the protective film can be made excellent in designability.

In the second surface 13b of the protective film-forming film 13, it is preferable that the maximum height difference between the highest portion of the convex portion and the deepest portion of the concave portion is 2 μm or less, for example, 1.5 μm or less and 1 μm. Any of the following may be sufficient. The protective film-forming film 13 and the protective film are particularly excellent in design.

The maximum height difference in the second surface 13b of the protective film-forming film 13 is, for example, the cross section of the protective film-forming composite sheet itself or the test piece of the protective film-forming composite sheet by the method described above. It can be obtained by forming and observing this cross section using a scanning electron microscope (SEM).

Here, the protective film-forming composite sheet 1A has been described, for example, for an adhesive layer and a protective film-forming film, but other embodiments such as a protective film-forming composite sheet 1B and a protective film-forming composite sheet 1C Also in the case of the composite sheet for forming a protective film, the pressure-sensitive adhesive layer and the film for forming a protective film are the same.

In the composite sheet for forming a protective film of the present invention, the thickness (for example, T _p ) of the film for forming a protective film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and 5 to 50 μm. It is particularly preferred. Since the thickness of the protective film-forming film is greater than or equal to the lower limit, a protective film having a higher protective ability can be formed. Since the thickness of the film for forming a protective film is less than or equal to the upper limit, excessive thickness is suppressed.

When the thickness of the protective film-forming film varies depending on the portion of the protective film-forming film, the minimum value of the thickness of the protective film-forming film may be equal to or greater than the lower limit, and even if the maximum value of the thickness of the protective film-forming film is equal to or less than the upper limit. do.

On the other hand, "the thickness of the protective film-forming film" means the thickness of the entire protective film-forming film. For example, the thickness of the protective film-forming film composed of multiple layers is the sum of all layers constituting the protective film-forming film. Means thickness.

The thickness of the protective film-forming film can be measured, for example, by observing the side surface or the cross section of the protective film-forming film using a scanning electron microscope (SEM).

The cross section of the film for forming a protective film can be formed by the same method as in the case of the cross section of the test piece of the support sheet and the composite sheet for forming a protective film described above, for example.

For example, by cutting out a test piece from a plurality of locations (e.g., 5 locations) of the composite sheet for forming a protective film by the method described above, in this test piece, the minimum and maximum values of the thickness of the film for forming a protective film are obtained, When the average value of these minimum and maximum values is further calculated from these values, the average value of the minimum value may be equal to or greater than the lower limit of the thickness of the film for forming a protective film, and the average value of the maximum value is the aforementioned film for forming a protective film. It may be less than or equal to the upper limit of the thickness of.

The film for protective film formation can be formed using a composition for forming a protective film containing the constituent material. For example, a protective film-forming film can be formed on a target site by coating the protective film-forming composition on the surface to be formed on the protective film-forming film and drying it as necessary. In the composition for forming a protective film, the content ratio between components that do not vaporize at room temperature is usually the same as the content ratio between the components in the film for forming a protective film.

Coating of the composition for formation of protection may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater. , A method of using various coaters such as a Mayer bar coater and a kiss coater.

Drying conditions of the composition for forming a protective film are not particularly limited, but when the composition for forming a protective film contains a solvent described later, it is preferable to heat-dry. In addition, the composition for forming a protective film containing a solvent is preferably dried at 70 to 130°C for 10 seconds to 5 minutes. However, when the composition for forming a protective film is thermosetting, it is preferable to dry the composition for forming a protective film so that the film for forming a protective film to be formed is not thermally cured.

Hereinafter, the protective film-forming film and the protective film-forming composition will be described in detail for each type.

○ Film for forming a thermosetting protective film

As a preferable film for thermosetting protective film formation, what contains a polymer component (A) and a thermosetting component (B) is mentioned, for example.

The polymer component (A) is a component that can be considered to be formed by a polymerization reaction of a polymerizable compound.

The thermosetting component (B) is a component capable of curing (polymerization) reaction using heat as a trigger of the reaction. On the other hand, in the present invention, the polymerization reaction also includes a polycondensation reaction.

The curing conditions at the time of thermosetting after affixing the film for forming a thermosetting protective film on the back surface of a semiconductor wafer are not particularly limited as long as the curing degree of the cured product sufficiently exhibits its function, and the film for forming a thermosetting protective film You just need to select it appropriately according to the type.

For example, the heating temperature during thermosetting of the thermosetting protective film forming film is preferably 100 to 200°C, more preferably 110 to 180°C, and particularly preferably 120 to 170°C. Further, the heating time at the time of curing is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.

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

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

[Polymer component (A)]

The polymer component (A) is a component for imparting film-forming properties, flexibility, and the like to the film for forming a thermosetting protective film.

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

Examples of the polymer component (A) include acrylic resins, polyesters, urethane resins, acrylic urethane resins, silicone resins, rubber resins, phenoxy resins, thermosetting polyimides, and acrylic resins.

Known acrylic polymers can be mentioned as the acrylic resin in the polymer component (A).

It is preferable that it is 10000-2000000, and, as for the weight average molecular weight (Mw) of an acrylic resin, it is more preferable that it is 100000-150,000. Since the weight average molecular weight of the acrylic resin is more than the above lower limit, the shape stability (stability with time during storage) of the film for forming a thermosetting protective film is improved. In addition, since the weight average molecular weight of the acrylic resin is less than or equal to the above upper limit, the film for forming a thermosetting protective film is easier to follow on the uneven surface of the adherend, and the occurrence of voids between the adherend and the film for forming a thermosetting protective film is more suppressed. .

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

It is preferable that it is -60 to 70 degreeC, and, as for the glass transition temperature (Tg) of an acrylic resin, it is more preferable that it is -30 to 50 degreeC. Since the Tg of the acrylic resin is more than the above lower limit, for example, the adhesion between the cured product (ie, the protective film) of the protective film forming film and the support sheet is suppressed, and the peelability of the support sheet is suitably improved. Further, since the Tg of the acrylic resin is equal to or less than the above upper limit, the adhesion between the film for forming a thermosetting protective film and the adherend of the protective film is improved.

Meanwhile, the Tg of the resin in the present specification is not limited to the acrylic resin, for example, using a differential scanning calorimeter (DSC), the temperature increase rate or the temperature decrease rate is 10°C/min, and between -70°C and 150°C. It can be obtained by changing the temperature of the object to be measured at and checking the inflection point.

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

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

Cycloalkyl esters of (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate;

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

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

(Meth)acrylate cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate;

Imide (meth)acrylate;

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

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

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

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

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

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

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

It is preferable that it is 1000-100000, and, as for the weight average molecular weight of the said thermoplastic resin, it is more preferable that it is 3000-80000.

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

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

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

In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the content of the polymer component (A) of the film for forming a thermosetting protective film) is the polymer component (A) Regardless of the kind of, it is preferably 5 to 85% by mass, more preferably 5 to 75% by mass, for example, 5 to 65% by mass, 5 to 50% by mass, and 10 to 35% by mass. Any one may be sufficient.

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

[Thermosetting component (B)]

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

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

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

(Epoxy thermosetting resin)

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

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

Epoxy resin (B1)

Known epoxy resins (B1) include, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene Type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher epoxy compounds.

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

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

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

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

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but in terms of the curability of the film for forming a thermosetting protective film and the strength and heat resistance of the protective film after curing, it is preferably 300 to 30,000, more preferably 300 to 10000, and , It is particularly preferably 300 to 3000.

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

It is preferable that it is 100-1000 g/eq, and, as for the epoxy equivalent of the epoxy resin (B1), it is more preferable that it is 150-950 g/eq.

In the present specification, "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.

Epoxy resin (B1) may be used alone or in combination of two or more, and when two or more are used in combination, combinations and ratios thereof can be arbitrarily selected.

·Heat curing agent (B2)

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

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

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

Among the thermal curing agents (B2), examples of the amine curing agent having an amino group include dicyandiamide.

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

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

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

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

Among the thermosetting agents (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 to 30000, It is more preferable that it is 400-10000, and it is especially preferable that it is 500-3000.

Among the thermal curing agents (B2), for example, the molecular weight of the non-resin component such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

The thermosetting agent (B2) may be used singly or in combination of two or more, and when two or more of them are used in combination, combinations and ratios thereof can be arbitrarily selected.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass, and 1 to 200 parts by mass based on 100 parts by mass of the epoxy resin (B1). It is more preferable and, for example, any one of 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 25 parts by mass, and 1 to 10 parts by mass may be used. Since the content of the thermosetting agent (B2) is more than the lower limit, the curing of the film for forming a thermosetting protective film is more likely to proceed. Further, since the content of the thermosetting agent (B2) is equal to or less than the upper limit, the moisture absorption rate of the film for forming a thermosetting protective film is reduced, and the reliability of the package obtained using the composite sheet for forming a protective film is further improved.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is the content of the polymer component (A). It is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, further preferably 40 to 150 parts by mass, for example, 45 to 100 parts by mass and 50 to 80 parts by mass, etc. It may be any one of. When the content of the thermosetting component (B) is in such a range, for example, the adhesion between the cured product of the film for forming a protective film and the support sheet is suppressed, and the peelability of the support sheet is improved.

[Hardening accelerator (C)]

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

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

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

When using the curing accelerator (C), in the composition (III-1) and the film for forming a thermosetting protective film, the content of the curing accelerator (C) is 0.01 to 10 parts by mass based on 100 parts by mass of the thermosetting component (B). It is preferable and it is more preferable that it is 0.1-7 mass parts. Since the content of the curing accelerator (C) is more than the lower limit, the effect of using the curing accelerator (C) is more remarkably obtained. In addition, since the content of the curing accelerator (C) is not more than the above upper limit, for example, the high polarity curing accelerator (C) moves to the adhesion interface side with the adherend in the film for forming a thermosetting protective film under high temperature and high humidity conditions and segregates. The effect of suppressing the formation of the protective film is enhanced, and the reliability of the semiconductor chip with the protective film obtained by using the composite sheet for forming a protective film is further improved.

[Filling material (D)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). When the film for forming a thermosetting protective film contains the filler (D), it becomes easier to adjust the water absorption rate and the adhesive force change rate within a target range. In addition, since the thermosetting protective film-forming film and the protective film contain a filler (D), it becomes easier to control the thermal expansion coefficient, and by optimizing the thermal expansion coefficient for the film for forming a thermosetting protective film or the object for which the protective film is formed, the composite for forming a protective film The reliability of the semiconductor chip with the protective film obtained using the sheet is further improved. Further, the film for forming a thermosetting protective film may contain the filler (D), thereby reducing the moisture absorption rate of the protective film or improving the heat dissipation property.

The filler (D) may be either an organic filler or an inorganic filler, but it is preferably an inorganic filler.

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

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

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

When using the filler (D), in the composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, the content of the filler (D) of the film for forming a thermosetting protective film ) Is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, for example, may be any one of 20 to 65% by mass, 30 to 65% by mass, and 40 to 65% by mass. . When the content of the filler (D) is within such a range, the adjustment of the thermal expansion coefficient becomes easier, and the strength of the protective film-forming film and the protective film is further improved.

[Coupling agent (E)]

The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using the coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion and adhesion of the film for forming a thermosetting protective film to an adherend can be improved. Further, by using the coupling agent (E), the cured product (protective film) of the film for forming a thermosetting protective film does not impair heat resistance and improves water resistance.

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

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

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

When using a coupling agent (E), in the composition (III-1) and the film for forming a thermosetting protective film, the content of the coupling agent (E) is 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B) It is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. Since the content of the coupling agent (E) is greater than or equal to the lower limit, a coupling agent (E) is used for improving the dispersibility of the filler (D) in the resin or improving the adhesion of the film for forming a thermosetting protective film to an adherend. The effect by is obtained more remarkably. Further, since the content of the coupling agent (E) is less than or equal to the upper limit, generation of outgas is more suppressed.

[Crosslinking agent (F)]

When using a polymer component (A) having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, which can be bonded to other compounds such as acrylic resin described above, is used, the composition (III- 1) and the film for thermosetting protective film formation may contain a crosslinking agent (F). The crosslinking agent (F) is a component for crosslinking by combining the functional group with another compound of the polymer component (A), and by crosslinking in this manner, the initial adhesive force and cohesive force of the film for forming a thermosetting protective film can be adjusted.

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

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

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

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

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

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

When using the crosslinking agent (F), the content of the crosslinking agent (F) in the composition (III-1) is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass based on 100 parts by mass of the polymer component (A). It is more preferable and it is especially preferable that it is 0.5-5 mass parts. Since the content of the crosslinking agent (F) is not less than the lower limit, the effect of using the crosslinking agent (F) is more remarkably obtained. Further, since the content of the crosslinking agent (F) is less than or equal to the upper limit, excessive use of the crosslinking agent (F) is suppressed.

[Energy ray curable resin (G)]

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

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

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

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

It is preferable that it is 100-30000, and, as for the weight average molecular weight of the said energy ray-curable compound, it is more preferable that it is 300-10000.

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

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

When using the energy ray-curable resin (G), the content of the energy ray-curable resin (G) relative to the total content of all components other than the solvent of the composition (III-1) is preferably 1 to 95% by mass, 5 It is more preferable that it is -90 mass %, and it is especially preferable that it is 10 to 85 mass %.

[Photopolymerization initiator (H)]

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

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

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

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

When using a photoinitiator (H), the content of the photoinitiator (H) in the composition (III-1) is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the energy ray-curable resin (G), and 1 to It is more preferable that it is 10 mass parts, and it is especially preferable that it is 2-5 mass parts.

[Coloring agent (I)]

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

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

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

Examples of the inorganic pigment include carbon black, cobalt pigment, iron pigment, chromium pigment, titanium pigment, vanadium pigment, zirconium pigment, molybdenum pigment, ruthenium pigment, platinum pigment, ITO (indium Tin oxide)-based dyes, ATO (antimony tin oxide)-based dyes, and the like.

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

When using the colorant (I), the content of the colorant (I) in the film for forming a thermosetting protective film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film, and adjusting the light transmittance of the protective film, printing visibility when laser printing is performed on the protective film can be adjusted. Further, by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film, the designability of the protective film can be improved or it is possible to make it difficult to show the grinding trace on the back surface of the semiconductor wafer. Taking this point into consideration, in the composition (III-1), the content ratio of the colorant (I) to the total content of all components other than the solvent (that is, the content of the colorant (I) in the film for forming a thermosetting protective film) is 0.1 It is preferable that it is -10 mass %, it is more preferable that it is 0.1-7.5 mass %, It is especially preferable that it is 0.1-5 mass %. Since the content of the colorant (I) is more than the lower limit, the effect of using the colorant (I) is more remarkably obtained.In addition, since the content of the colorant (I) is less than or equal to the upper limit, the film for forming a thermosetting protective film Excessive decrease in light transmittance is suppressed.

[Universal Additive (J)]

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

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

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

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

[menstruum]

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

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

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

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

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

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

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

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

A method of mixing each component during mixing is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc.; Mixing using a mixer; What is necessary is just to select appropriately from known methods, such as a method of applying ultrasonic waves and mixing.

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

○ Energy ray-curable protective film formation film

Examples of the film for forming an energy ray-curable protective film include those containing the energy ray-curable component (a), and preferably contain the energy ray-curable component (a) and a filler.

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

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

For example, it is preferable that the illuminance of the energy ray at the time of curing the energy ray-curable protective film-forming film is 120 to 280 mW/cm 2. In addition, it is preferable that the amount of light of the energy ray at the time of curing is 100 to 1000 mJ/cm 2.

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

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

[Energy ray curable component (a)]

The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and provides film-forming properties or flexibility to the energy ray-curable protective film-forming film, and is also a component for forming a hard protective film after curing. .

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 compound (a2) having an energy ray-curable group and a molecular weight of 100-80000. . The polymer (a1) may be at least partially crosslinked with a crosslinking agent or may not be crosslinked.

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

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

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

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

・Acrylic polymer (a11) having a functional group

Examples of the acrylic polymer (a11) having a functional group include those obtained by copolymerization of an acrylic monomer having the functional group and an acrylic monomer not having the functional group. In addition to these monomers, a monomer other than the acrylic monomer (non An acrylic monomer) may be copolymerized.

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

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

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

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

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

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

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

In addition, as an acrylic monomer having no functional group, for example, alkoxyalkyl groups such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate Containing (meth)acrylic acid ester; (Meth)acrylic acid esters having an aromatic group including (meth)acrylate aryl esters such as phenyl (meth)acrylate; Non-crosslinkable (meth)acrylamide and derivatives thereof; And (meth)acrylic acid esters having a non-crosslinkable tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.

The acrylic monomers which do not have the functional groups constituting the acrylic polymer (a11) may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof may be arbitrarily selected.

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

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

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

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

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

Energy ray-curable compound (a12)

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

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

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

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

An acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate, etc. are mentioned.

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

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

In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is 20 to 120 mol It is preferable that it is a %, it is more preferable that it is 35-100 mol%, and it is especially preferable that it is 50-100 mol%. When the content ratio is within such a range, after curing, the adhesive force of the protective film becomes larger. On the other hand, when the energy ray-curable compound (a12) is a monofunctional compound (having one group per molecule), the upper limit of the content ratio is 100 mol%, but the energy ray-curable compound (a12) is different. In the case of a functional (having two or more of the above groups per molecule), the upper limit of the content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000 to 2000000, more preferably 300000 to 150,000.

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

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

(Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 800,000)

Among the compounds (a2) having an energy ray-curable group having a molecular weight of 100 to 800,000, the energy ray-curable group includes a group containing an energy ray-curable double bond, and preferable examples include a (meth)acryloyl group and a vinyl group. I can.

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

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

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

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

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

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

It is preferable that it is 100-30000, and, as for the weight average molecular weight of the said compound (a2), it is more preferable that it is 300-10000.

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

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

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

The polymer (b) may be at least partially cross-linked with a cross-linking agent, or may not be cross-linked.

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

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

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

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

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

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

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

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

And (meth)acrylate cycloalkenyloxyalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate.

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

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

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

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

As the polymer (b) which does not have the energy ray-curable group at least partially crosslinked with a crosslinking agent, for example, a reactive functional group in the polymer (b) reacts with a crosslinking agent.

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

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

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

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10000 to 2000000, and more preferably 100000 to 150,000, from the viewpoint of better film forming properties of the composition (IV-1). Here, "weight average molecular weight" is as previously described.

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

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

When the composition (IV-1) contains the polymer (a1), the compound (a2) and the polymer (b) having no energy ray-curable group, in the composition (IV-1), the content of the compound (a2) Silver is preferably 10 to 400 parts by mass, and more preferably 30 to 350 parts by mass, based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group.

In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) not having an energy ray-curable group to the total content of components other than the solvent (that is, formation of an energy ray-curable protective film The total content of the energy ray-curable component (a) and the polymer (b) not having an energy ray-curable group) of the film is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and 20 to It is particularly preferably 70% by mass. When the ratio of the content of the energy ray-curable component is within such a range, the energy ray-curable property of the film for forming an energy ray-curable protective film becomes better.

In addition to the energy ray-curable component, the composition (IV-1) may contain one or two or more selected from the group consisting of a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general-purpose additive, depending on the purpose. do.

For example, by using the composition (IV-1) containing the energy ray-curable component and the thermosetting component, the energy ray-curable protective film-forming film formed is improved in adhesion to the adherend by heating, and this energy ray The strength of the protective film formed from the film for forming a curable protective film is also improved.

In addition, the film for forming an energy ray-curable protective film formed by using the composition (IV-1) containing the energy ray-curable component and the colorant is the same as when the film for forming a thermosetting protective film described above contains the colorant (I). Expresses the effect.

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

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

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

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

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

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

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

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

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

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent, and the compounded component may be diluted beforehand, and the solvent may be mixed with these compounded components without pre-diluting any compounded component other than the solvent. You may use it by doing.

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

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

○ Film for forming a non-curable protective film

The film for forming a non-curable protective film does not show any change in properties due to curing, but in the present invention, it is assumed that the protective film is formed in a step affixed to a target location, such as the back surface of a semiconductor wafer.

As a preferable film for forming a non-curable protective film, those containing a thermoplastic resin are exemplified.

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

As the composition for forming a non-curable protective film, for example, the composition for forming a non-curable protective film (V-1) containing the thermoplastic resin (in this specification, it may be simply abbreviated as ``composition (V-1)''). ), etc.

[Thermoplastic resin]

The thermoplastic resin is not particularly limited.

More specifically, the thermoplastic resin is not curable, such as acrylic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. as contained components of the above-described composition (III-1). The same thing as resin can be mentioned.

The thermoplastic resins contained in the composition (V-1) and the film for forming a non-curable protective film may be only one type, may be two or more types, and in the case of two or more types, combinations and ratios thereof can be arbitrarily selected.

In the composition (V-1), the ratio of the content of the thermoplastic resin to the total content of components other than the solvent (that is, the content of the thermoplastic resin in the film for forming a non-curable protective film) is preferably 5 to 90% by mass, , For example, any of 10 to 80% by mass and 20 to 70% by mass may be used.

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

For example, the film for forming a non-curable protective film formed by using the composition (V-1) containing the thermoplastic resin and the colorant has the same effect as when the film for forming a thermosetting protective film described above contains the colorant (I). Express.

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

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

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

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

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

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

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

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

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

In the case of using a solvent, the solvent may be mixed with any compounding component other than the solvent, and the compounded component may be diluted beforehand, and the solvent may be mixed with these compounded components without pre-diluting any compounded component other than the solvent. You may use it by doing.

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

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

◎Other floor

The support sheet may be provided with other layers such as the intermediate layer in addition to the base material and the pressure-sensitive adhesive layer within a range that does not impair the effects of the present invention.

In addition, the composite sheet for forming a protective film may be provided with other layers in addition to the base material, the pressure-sensitive adhesive layer and the film for forming a protective film within the range not impairing the effect of the present invention, and the other layer in this case is a support sheet The other layers may be provided, and may be disposed without direct contact with the support sheet.

The other layer may be arbitrarily selected according to the purpose, and the type is not particularly limited.

In one embodiment of the support sheet and the composite sheet for forming a protective film, for example, the pressure-sensitive adhesive layer is non-energy ray-curable, and the pressure-sensitive adhesive layer comprises at least the acrylic polymer and a crosslinking agent having a structural unit derived from an alkyl (meth)acrylate. Containing, in the pressure-sensitive adhesive layer, the content of the crosslinking agent relative to 100 parts by mass of the acrylic polymer content is 0.3 to 50 parts by mass, and the maximum height roughness (Rz) of the first surface of the substrate is 0.01 to 8 µm. Can be mentioned.

In one embodiment of the support sheet and the composite sheet for forming a protective film, for example, the pressure-sensitive adhesive layer is non-energy ray-curable, and the pressure-sensitive adhesive layer comprises at least the acrylic polymer and a crosslinking agent having a structural unit derived from an alkyl (meth)acrylate. Containing, in the pressure-sensitive adhesive layer, the content of the crosslinking agent with respect to 100 parts by mass of the acrylic polymer is 0.3 to 50 parts by mass, and the acrylic polymer is a structural unit derived from an alkyl (meth)acrylate having 4 or more carbon atoms in the alkyl group; And a structural unit derived from a hydroxyl-containing monomer, and the maximum height roughness (Rz) of the first surface of the substrate is 0.01 to 8 µm.

In one embodiment of the support sheet and the composite sheet for forming a protective film, for example, the pressure-sensitive adhesive layer is non-energy ray-curable, and the pressure-sensitive adhesive layer comprises at least the acrylic polymer and a crosslinking agent having a structural unit derived from an alkyl (meth)acrylate. Containing, in the pressure-sensitive adhesive layer, the content of the crosslinking agent with respect to 100 parts by mass of the acrylic polymer is 0.3 to 50 parts by mass, and the acrylic polymer is a structural unit derived from an alkyl (meth)acrylate having 4 or more carbon atoms in the alkyl group; , A structural unit derived from a hydroxyl group-containing monomer, and in the acrylic polymer, the content of the constitutional unit derived from the hydroxyl group-containing monomer is 1 to 35% by mass with respect to the total amount of the constitutional unit, and the first side of the substrate What is the maximum height roughness Rz of 0.01-8 micrometers is mentioned.

In one embodiment of the support sheet and the composite sheet for forming a protective film, for example, the pressure-sensitive adhesive layer is non-energy ray-curable, and the pressure-sensitive adhesive layer comprises at least the acrylic polymer and a crosslinking agent having a structural unit derived from an alkyl (meth)acrylate. And, in the pressure-sensitive adhesive layer, the content of the crosslinking agent with respect to 100 parts by mass of the acrylic polymer is 0.3 to 50 parts by mass, and the acrylic polymer is a structural unit derived from an alkyl (meth)acrylate having 4 or more carbon atoms in the alkyl group; It has a structural unit derived from a hydroxyl group-containing monomer, and in the acrylic polymer, the content of the structural unit derived from the hydroxyl group-containing monomer is 1 to 35% by mass with respect to the total mass of the structural unit, the crosslinking agent is an isocyanate crosslinking agent, and It is mentioned that the maximum height roughness Rz of the first surface of the substrate is 0.01 to 8 μm.

◇Method of manufacturing composite sheet for forming a protective film

In the composite sheet for forming a protective film, for example, a substrate, an adhesive layer, and a film for forming a protective film are laminated in this order in their thickness direction to produce a laminated sheet (in this specification, ``Laminated sheet production Process (1)") and a process of storing the laminated sheet while pressing in its thickness direction (in this specification, it may be referred to as a ``laminated sheet preservation process'') In this specification, it can be manufactured by "the manufacturing method (S1)" in some cases).

The method of forming each layer (substrate, pressure-sensitive adhesive layer, and film for forming a protective film) is as described above.

Hereinafter, the manufacturing method (S1) will be described in more detail for each step.

◎ Manufacturing method (S1)

<<Laminated sheet manufacturing process (1)>>

In the said laminated sheet manufacturing process (1), a laminated sheet|seat comprised by laminating a base material, an adhesive layer, and a film for protective film formation in these thickness direction in this order is produced.

In this step, for example, by laminating each of the above-described layers (substrate, pressure-sensitive adhesive layer, film for forming a protective film, etc.) in a corresponding positional relationship, lamination having the same lamination structure as the composite sheet for forming a protective film of interest. Make a sheet.

On the other hand, in the present specification, the term "laminated sheet" means that it has the same laminated structure as the composite sheet for forming a protective film for the same purpose as described above, and has not performed the laminated sheet preservation step unless otherwise noted. do.

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

On the other hand, for example, when a protective film-forming film is additionally laminated on the pressure-sensitive adhesive layer laminated on the substrate, it is possible to directly form the protective film-forming film by coating the protective film-forming composition on the pressure-sensitive adhesive layer. . Layers other than the film for forming a protective film can also be laminated on the pressure-sensitive adhesive layer by the same method using the composition for forming this layer. In this way, in the case of forming a continuous two-layer laminated structure using any one composition, it is possible to form a new layer by further coating the composition on the layer formed from the composition. However, the layer to be laminated later among these two layers is formed in advance using the composition on another release film, and the exposed side of the formed layer opposite to the side in contact with the release film is exposed to the remaining layers already formed. It is preferable to form a continuous two-layer laminated structure by bonding with the surface. At this time, it is preferable to apply the composition to the peeling-treated surface of the peeling film. The release film may be removed as necessary after formation of the laminated structure.

For example, a composite sheet for forming a protective film (a composite sheet for forming a protective film in which a support sheet is a laminate of a substrate and an adhesive layer) is prepared by laminating an adhesive layer on a substrate and a film for forming a protective film on the adhesive layer. In the case of application, the pressure-sensitive adhesive composition is coated on the substrate, and if necessary, the pressure-sensitive adhesive layer is laminated on the substrate, and a protective film-forming composition is separately applied on the release film, and if necessary, the release film is dried. A film for forming a protective film is formed on the top. And the said laminated sheet is obtained by bonding the exposed surface of this film for protective film formation with the exposed surface of the adhesive layer laminated on a base material, and laminating the film for protective film formation on the adhesive layer.

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

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

In this way, since all layers other than the base material constituting the composite sheet for forming a protective film can be formed in advance on a release film and laminated by a method of bonding to the surface of the target layer, such a process is adopted as necessary. The above-described laminated sheet may be manufactured by appropriately selecting a layer to be described.

For example, a composite sheet for forming a protective film is usually stored in a state in which a release film is adhered to the surface of the outermost layer (for example, a film for forming a protective film) opposite to the supporting sheet. Therefore, a composition for forming a layer constituting an outermost layer, such as a composition for forming a protective film, is applied on this release film (preferably, the peeling treatment surface thereof), and dried as necessary to form the outermost layer on the release film. A layer constituting the layer is formed, and the remaining layers are laminated on the exposed side opposite to the side in contact with the release film of this layer by any of the above-described methods, and are bonded without removing the release film. Even if it remains, the said laminated sheet is obtained.

When the composite sheet for forming a protective film is provided with the other layer, a step of forming the other layer may be appropriately added so as to be at an appropriate placement position at an appropriate timing in the above-described laminated sheet manufacturing process (1).

The shape of the laminated sheet produced in the laminated sheet production process (1) is not particularly limited. For example, in order to wind up in a roll shape, a preferable long laminated sheet may be produced, but a laminated sheet having a shape other than that of the long may be produced.

<<laminated sheet preservation process>>

In the laminated sheet preservation step, the laminated sheet is stored while being pressed in the thickness direction.

In this step, as a method of preserving the laminated sheet while pressing it, for example, the long laminated sheet is wound in a roll shape, and the wound laminated sheet is left as it is, and the pressure generated by winding is applied to the laminated sheet. A method of preserving while applying to one side or both sides of the product; And a method of storing the elongated laminated sheet while applying pressure to one or both sides of the laminated sheet in an unfolded state without being wound up in a roll shape.

When winding up a long laminated sheet in a roll shape, it is preferable to wind up the laminated sheet in the longitudinal direction.

When winding up a laminated sheet, for example, the winding tension is preferably 150 to 170 N/m, the winding speed is preferably 45 to 55 m/min, and the taper rate (reduction rate) of the winding tension is 85 to 95 It is preferably %. By employing such winding conditions, the laminated sheet can be pressurized and stored at a more suitable pressure. Such winding conditions are particularly preferable to apply to a laminated sheet having a thickness of 100 to 300 µm, a width of 300 to 500 mm, and a length of 40 to 60 m, for example, but the size of the laminated sheet is not limited thereto.

The laminated sheet may be wound under normal temperature or room temperature, for example, or may be wound under the same temperature conditions as when the wound laminated sheet is stored under heat and pressure as described later.

The laminated sheet wound up in a roll shape may be stored at room temperature or at room temperature, but is preferably stored while heating. By heat-pressing storage in this way, a composite sheet for forming a protective film is obtained, which is superior in the lamination property of the pressure-sensitive adhesive layer and the film for forming a protective film, and more excellent in printing visibility through the supporting sheet of the protective film or the film for forming a protective film.

When the laminated sheet is wound in a roll shape, the heating temperature at the time of storage is not particularly limited, but it is preferably 53 to 75°C, more preferably 55 to 70°C, and particularly preferably 57 to 65°C.

The storage time when the laminated sheet is wound up in a roll shape is not particularly limited, but is preferably 24 to 720 hours (1 to 30 days), more preferably 48 to 480 hours (2 to 20 days), and 72 to It is particularly preferred that it is 240 hours (3-10 days).

In a laminated sheet wound in a roll shape, for example, a protective film-forming film and a support sheet are processed into a specific shape, and a plurality of laminates of the thus-processed support sheet and protective film-forming film are placed on the side of the protective film-forming film. WHEREIN: While being pasted on a long peeling film, you may be arrange|positioned by aligning in the longitudinal direction of this peeling film. It is preferable that the film for protective film formation in this case has the same or substantially the same planar shape (usually, circular shape) as the semiconductor wafer. In addition, it is preferable that the support sheet in this case has the same or substantially the same outer periphery shape as the jig for fixing the support sheet among the dicing devices. In this case, it is preferable that a strip-shaped sheet is formed in the vicinity of the periphery in the width direction among the bonding surfaces of the laminate of the release film so as not to overlap with the laminate. This sheet is for suppressing the occurrence of a step (in this specification, it may be referred to as "lamination trace") on the surface of the laminate when the laminated sheet is wound in a roll shape. The lamination trace is that the lamination position of the lamination product (the laminate of the processed supporting sheet and the protective film forming film) in the roll of the lamination sheet does not coincide in the radial direction of the roll, so that high pressure is applied to the surface of the lamination material. It is caused by burden. When the sheet is formed in the vicinity of the periphery, such high pressure is not applied to the surface of the laminate, and generation of the lamination trace is suppressed.

In the case where the elongate laminated sheet is not wound in a roll shape and is in an unfolded state, and the laminated sheet is not long, it is preferable to further laminate and store a plurality of these laminated sheets. And, in the case of laminating the laminated sheets in this way, it is preferable that the directions of the plurality of laminated sheets and the position of the periphery are aligned with each other.

The shape and size of the non-long laminated sheet (that is, the single-leaf laminated sheet) are not particularly limited. For example, in accordance with the shape and size of the semiconductor wafer and the shape and size of the jig for fixing the support sheet among the dicing apparatus, the laminated sheet may be It is preferable that the shape and size are adjusted.

The laminated sheet in a laminated state may be stored at room temperature or at room temperature, but is preferably stored while heating. By heat-pressing storage in this way, a composite sheet for forming a protective film is obtained, which is superior in the lamination property of the pressure-sensitive adhesive layer and the film for forming a protective film, and more excellent in printing visibility through the supporting sheet of the protective film or the film for forming a protective film.

In addition, both the heating temperature and storage time in the case of pressurized storage of the laminated sheet in a laminated state can be the same as in the case of winding the laminated sheet in a roll shape.

In the manufacturing method (S1), by releasing the pressure of the laminated sheet and heating as necessary after the completion of the laminated sheet preservation step, the target composite sheet for forming a protective film is obtained.

In the lamination sheet manufacturing process (1) of the manufacturing method (S1), the order of lamination (bonding) of the substrate, the pressure-sensitive adhesive layer, and the protective film-forming film is not particularly limited, but a supporting sheet is prepared in advance (adhesive on the substrate in advance). Layers are laminated) to separately prepare a protective film-forming film in advance, and when the protective film-forming film is laminated on the support sheet, either or both of the support sheet and the protective film-forming film are alone, before laminating them. You may pressurize and store in the same manner as in the case of the laminated sheet described above. By individually pressurizing the support sheet before lamination, it is possible to more effectively suppress the occurrence of the non-bonded region between the substrate and the pressure-sensitive adhesive layer. In addition, by separately pressing and storing the protective film-forming film before lamination, the unevenness of the protective film-forming film and the pressure-sensitive adhesive layer side (second surface) of the protective film is reduced (the smoothness increases), and the protective film-forming film and the protective film are The design is improved.

That is, in the composite sheet for forming a protective film, for example, by laminating a film for forming a protective film on the pressure-sensitive adhesive layer of a support sheet in which a substrate and an adhesive layer are laminated, the substrate, the pressure-sensitive adhesive layer, and the film for forming a protective film are in this order, Process of producing a laminated sheet formed by being laminated in the thickness direction (in this specification, it may be referred to as ``laminated sheet production process (2)''), and storage while pressing the laminated sheet in the thickness direction It has a process (preservation process) to perform, and either or both of the support sheet and the film for forming a protective film are prepared before the laminated sheet production process (2) (that is, before the support sheet and the film for forming a protective film are laminated). The process of preserving while pressing in the thickness direction (in this specification, the process of preserving the support sheet is referred to as the ``support sheet preservation process'', and the process of preserving the film for protective film formation is called the ``film preservation process for protective film formation'' It can be manufactured by a manufacturing method (in this specification, it may be called "production method (S2)" in some cases) further having.

◎Manufacturing method (S2)

The manufacturing method (S2) is performed by performing the lamination sheet manufacturing step (2) as the lamination sheet manufacturing step (1) described above, and adding either or both of the supporting sheet storage step and the film storage step for forming a protective film. Except for the point, it is the same as the manufacturing method (S1) described above.

<<Laminated sheet manufacturing process (2)>>

In the laminated sheet manufacturing process (2), as described above, a support sheet is prepared in advance, a protective film-forming film is separately prepared, and a protective film-forming film is laminated on the support sheet. It is the same as the laminated sheet production process (1) in the production method (S1) except that is limited.

<<support sheet preservation process, film preservation process for protective film formation>>

The support sheet preservation process and the film preservation process for forming a protective film can be performed in the same manner as the laminated sheet preservation process in the production method (S1), except that the object to be stored is not a laminated sheet but a support sheet or a film for forming a protective film. .

In this case, for example, the storage time of the supporting sheet and the film for forming a protective film is independently 24 to 720 hours (1 to 30 days) and 48 to 480 hours (2 to 20 days) as in the case of the laminated sheet. And 72 to 240 hours (3 to 10 days).

On the other hand, the support sheet preservation process and the film preservation process for forming a protective film are added to change the object to be preserved as described above, and also change the preservation time of the object to be preserved (support sheet or film for forming a protective film), and these changes Other than that, you may perform similarly to the laminated sheet preservation process in manufacturing method (S1).

In this case, for example, the storage time of the supporting sheet and the film for forming a protective film is independently 12 to 720 hours (0.5 to 30 days), 12 to 480 hours (0.5 to 20 days), and 12 to 240 hours (0.5 To 10 days). However, this is an example of the storage time.

One aspect of the present invention is a step of preparing a first laminated sheet comprising a substrate, an adhesive layer, and a first release film in this order, and the pressure-sensitive adhesive layer side surface of the substrate is an uneven surface,

It is a manufacturing method of a supporting sheet including a step of storing the first laminated sheet at 53 to 75°C for 24 to 720 hours.

In addition, another aspect of the present invention is provided with a substrate, a pressure-sensitive adhesive layer and a first release film in this order, the first laminated sheet in which the side of the pressure-sensitive adhesive layer of the substrate is an uneven surface, a third release film, and a film for forming a protective film And a step of preparing a laminated film provided with a second release film in this order,

A step of storing the first laminated sheet at 53 to 75°C for 24 to 720 hours,

The first release film and the second release film are removed, and the exposed surface of the pressure-sensitive adhesive layer and the exposed surface of the protective film-forming film are bonded to each other, and the substrate, the pressure-sensitive adhesive layer, the protective film-forming film, and the third peeling A process of manufacturing a second laminated sheet having a film in this order, and

This is a method for producing a composite sheet for forming a protective film including a step of storing the second laminated sheet at 53 to 75°C for 24 to 720 hours.

In another aspect of the present invention, in the method for manufacturing the composite sheet for forming a protective film, the step of bonding the exposed surface of the pressure-sensitive adhesive layer and the exposed surface of the film for forming a protective film is 0.3 to 75°C. It is carried out while pressing at a pressure of 0.8 MPa.

In addition, another aspect of the present invention is in the manufacturing method of the composite sheet for forming a protective film, wherein the first laminated sheet, the laminated film, and the second laminated sheet are each a long laminated sheet or a laminated film, the first Each of the laminated sheet and the second laminated sheet is wound up and stored in a roll shape in the storing step.

Example

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

<Materials for manufacturing the composition for forming a protective film>

The raw materials used for producing the composition for forming a protective film are shown below.

Polymer component (A)

(A)-1: Acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) (weight average molecular weight of 370000, glass transition temperature of 6°C

· Thermosetting component (B1)

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

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

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

·Heat curing agent (B2)

(B2)-1: Dicyandiamide ("Adeka Hardener EH-3636AS" manufactured by ADEKA, a thermally active latent epoxy resin curing agent, active hydrogen content 21 g/eq)

·Hardening accelerator (C)

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

·Filling material (D)

(D)-1: Silica filler ("SC2050MA" manufactured by Admatex, a silica filler surface-modified with an epoxy compound, average particle diameter 0.5 µm)

·Coupling agent (E)

(E)-1:3-aminopropyltrimethoxysilane ("A-1110" manufactured by NUC)

・Coloring agent (I)

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

[Example 1]

<Manufacture of support sheet>

(Preparation of adhesive composition (I-4))

It contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate crosslinking agent (``Takenate D110N'' manufactured by Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)), and as a solvent, methyl ethyl ketone, A specific energy ray-curable pressure-sensitive adhesive composition (I-4) having a solid content concentration of 30% by mass containing a mixed solvent of toluene and ethyl acetate was prepared. The acrylic polymer is a precopolymer having a weight average molecular weight of 800000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass).

(Manufacture of support sheet)

Using the first release film ("SP-PET381031" manufactured by Lintec, 38 µm in thickness), in which one side of the polyethylene terephthalate film was peeled off by silicone treatment, the pressure-sensitive adhesive composition (I) obtained above was used on the release-treated side -4) was applied, followed by heating and drying at 120° C. for 2 minutes to form a non-energy ray-curable pressure-sensitive adhesive layer. At this time, conditions were set so that the thickness of an adhesive layer might be 4 micrometers, and the adhesive composition (I-4) was coated.

A substrate in which one surface is an uneven surface and the other is a smooth surface (glossy surface) by rotating and pressing the uneven surface of a metal roll on one surface of a polypropylene film (manufactured by Mitsubishi Resin, thickness 80 μm) while heating Produced. The maximum height roughness (Rz) was measured in accordance with JIS B 0601:2013 about the uneven surface of this substrate, and it was 5 µm.

Subsequently, by bonding the uneven surface of the substrate to the exposed surface of the pressure-sensitive adhesive layer obtained above, a first laminated sheet formed by laminating the substrate, the pressure-sensitive adhesive layer, and the first release film in this order in their thickness direction was obtained. The width of the obtained first laminated sheet (that is, the width of the substrate and the pressure-sensitive adhesive layer) was 400 mm, and the length was 250 m.

Next, the first laminated sheet having a total size of 400 mm x 250 m obtained above was taken as a winding direction in the length direction under conditions of a winding tension of 160 N/m, a winding speed of 50 m/min, and a taper rate of 90% of the winding tension. It was wound around an 88 mm ABS resin core and wound up in a roll shape. At this time, the first laminated sheet was wound up with the substrate facing outward in the radial direction of the roll (that is, bringing the first release film into contact with the core).

Subsequently, this roll-shaped 1st laminated sheet was left standing for 7 days (168 hours) in an air atmosphere and 60 degreeC temperature conditions.

By the above, a support sheet was obtained.

With respect to this support sheet, immediately, an evaluation was performed regarding a non-bonded region between the substrate and the pressure-sensitive adhesive layer described later. In addition, this support sheet was used for production of a composite sheet for forming a protective film to be described later.

<Production of composite sheet for protective film formation>

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

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) was dissolved or dispersed in a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate, and stirred at 23° C. to obtain a composition (III-1) for forming a thermosetting protective film having a solid content of 51% by mass. Got it. On the other hand, all the blending amounts shown here are solid content.

(Production of protective film formation film)

A release film (3rd release film, "SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 µm), in which one side of the polyethylene terephthalate film was peeled off by silicone treatment, was used, and a knife coater was used for the release treatment surface. Then, the composition for forming a protective film (III-1) obtained above was applied and dried at 100° C. for 2 minutes to prepare a film for forming a thermosetting protective film having a thickness of 25 μm.

Moreover, by bonding the peeling-treated surface of the peeling film (2nd peeling film, "SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) to the exposed surface of the obtained protective film forming film on the side not provided with the third release film , A laminated film provided with a second release film on one side of the film for forming a protective film, and a third release film on the other side was obtained. The width of the obtained laminated film (that is, the width of the film for forming a protective film, the second release film, and the third release film) was 400 mm.

(Production of composite sheet for forming a protective film)

One set (two) rolls of 5 cm in diameter and composed of heat-resistant silicone rubber having a hardness of 50 degrees in a region of a depth of 3 mm from the surface thereof were prepared.

The first release film was removed from the pressure-sensitive adhesive layer of the support sheet obtained above. Moreover, the 2nd peeling film was removed from the laminated film obtained above.

And, the exposed surface of the pressure-sensitive adhesive layer formed by removing the first release film and the exposed surface of the protective film-forming film formed by removing the second release film are made to face each other, and these supporting sheets and the film for forming a protective film are polymerized. Thus, the laminate was heated and pressurized (heat laminated) at a pressure of 0.5 MPa by passing through the gap between the rolls set at a temperature of 60°C at a speed of 0.3 m/min, while the laminate was formed. Thereby, the second laminated sheet having the same laminated structure as the target composite sheet for forming a protective film, constituted by stacking the substrate, the pressure-sensitive adhesive layer, the film for forming a protective film, and the third release film in this order in the thickness direction thereof ( A composite sheet for forming a protective film before storage) was prepared.

In the obtained second laminated sheet, the width (that is, the width of the support sheet) was 400 mm.

Subsequently, the second laminated sheet having a total size of 400 mm x 250 m obtained above is taken as the direction in which the longitudinal direction is wound, the winding tension is 160 N/m, the winding speed is 50 m/min, and the taper rate of the winding tension is 90%. Then, it was wound around a core of ABS resin and wound up in a roll shape. At this time, the second laminated sheet was wound up with the substrate facing outward in the radial direction of the roll (that is, bringing the third release film into contact with the core).

Subsequently, this roll-shaped second laminated sheet was left standing for 7 days (168 hours) under a temperature condition of 60°C in an air atmosphere.

By the above, the composite sheet for forming a protective film of the present invention having the structure shown in Fig. 2 was obtained.

Next, after ending storage under such heating and pressing conditions, the following items were evaluated for the composite sheet for forming a protective film of the present invention.

<Evaluation of supporting sheet and composite sheet for forming protective film>

(Evaluation of the presence or absence of a non-bonded region between the substrate and the pressure-sensitive adhesive layer and the interlayer distance)

A test piece having a size of 3 mm x 3 mm was cut out from five locations of the composite sheet for forming a protective film obtained above. The cut-out positions of these five places were set as one location corresponding to the center of the circular protective film-forming film, and 4 locations corresponding to the location of the target object substantially in the vicinity of the peripheral edge. Of these five cutout positions, the distance between the centers of one location corresponding to the center and the other four locations in the vicinity of the periphery was 100 mm.

Using a single-sided sample preparation device ("cross section polisher SM-09010" manufactured by JEOL), the intermittent shutter conditions were set to "in" 10 seconds and "out" 5 seconds, and the voltage of the ion source was set to 3 kV. The polishing time was set to 24 hours, and the cross section was formed from the test piece. The newly formed cross section was only one side per test piece.

Using a scanning electron microscope (SEM), the newly formed cross section of these five test pieces was observed, and the presence or absence of a non-bonding area|region between a base material and an adhesive layer was confirmed. And when there was a non-bonding area|region, the number and the maximum value (d1) of the interlayer distance were measured.

At this time, the observation area of the cross section of the test piece is an area of 1 mm in the center of the cross section in the width direction (that is, an area of 1 mm in the width direction centering on the midpoints of the two ends in the width direction of the cross section) I did it.

On the other hand, in the case of measuring the interlayer distance, a cross section is formed in the composite sheet for forming a protective film in the same manner as in the case of the above-described test piece, and in this cross section, the maximum value of the interlayer distance between the substrate and the pressure-sensitive adhesive layer (d1 ) Was measured.

And evaluation was performed about the non-bonded area|region between a base material and a pressure-sensitive adhesive layer according to the following criteria. Table 1 shows the results.

(Evaluation of the number of non-bonded areas)

A: The number of non-bonded areas is 5 or less.

B: The number of non-bonded areas is 6 to 9.

C: The number of non-bonded areas is 10 or more.

(Evaluation of the maximum value (d1) of the interlayer distance)

A: There is no non-bonding area, or the maximum value (d1) of the interlayer distance is less than 0.1 µm.

B: There is a non-bonded area, but the maximum value d1 of the interlayer distance is 0.1 to 0.5 µm.

C: There is a non-bonding region, and the maximum value d1 of the interlayer distance is greater than 0.5 µm.

(Evaluation of print visibility of protective film)

The third release film was removed from the composite sheet for forming a protective film obtained above, and the exposed surface of the film for forming a protective film (the surface opposite to the side of the adhesive layer) was affixed to the back surface of an 8-inch semiconductor wafer. At this time, the affixing was performed using a tape mounter ("RAD2700" manufactured by Lintec). Thereby, a 1st laminated structure comprised by laminating a base material, an adhesive layer, a film for protective film formation, and a semiconductor wafer in these thickness directions in this order was produced.

Then, using a laser printing device ("CSM300M" manufactured by EO Technics), of the film for forming a protective film in the first laminated structure, the surface (second surface) on the side of the pressure-sensitive adhesive layer is irradiated with laser light through a support sheet to Did. At this time, characters having a size of 0.3 mm × 0.2 mm were printed.

Next, the printing (laser printing) of this film for forming a protective film was visually observed through a support sheet, and the visibility of the printing (character) was evaluated according to the following criteria. Table 1 shows the results. The printing visibility of the film for forming a protective film evaluated here can be considered to be equivalent to the printing visibility of the protective film.

A: The print is clear and can be easily recognized.

B: The factor is slightly cloudy and cannot be easily recognized.

C: The argument is unclear and cannot be recognized.

Subsequently, the support sheet (substrate and pressure-sensitive adhesive layer) was peeled from this film for forming a protective film. And using an optical microscope (made by Keyence Corporation), the thickness of the line of the print (character) formed on the film for protective film formation was measured. As a result, the thickness of the line was 40 µm or more, and it was clearly printed.

(Evaluation of adhesion between substrate and pressure-sensitive adhesive layer)

According to JIS K 5600-5-6, 100 grids were applied to the pressure-sensitive adhesive layer of the support sheet in a grid shape of 1 mm in width and length by a rotary cutter, and an adhesive tape (Cellotape [manufactured by Nichi Reflector, registered trademark]) was compressed. Thereafter, when the adhesive tape was peeled from 0.5 to 1.0 seconds at an angle of about 60°, a test was performed for the adhesion between the substrate and the adhesive layer by counting the number of grids remaining in the 100 grids. The evaluation of adhesion was performed according to the following criteria. And evaluation was performed on the adhesion between the base material and the pressure-sensitive adhesive layer according to the following criteria. Table 1 shows the results.

A: The number of remaining grids is 90 or more.

B: The number of remaining grids is 70 or more and less than 90.

C: The number of remaining grids is less than 70.

<Production of supporting sheet and composite sheet for forming protective film, evaluation of supporting sheet and composite sheet for forming protective film>

[Example 2]

In the case of Example 1, the support sheet was prepared in the same manner as in Example 1, except that the roll-shaped support sheet was left standing in an air atmosphere under a temperature condition of 60°C for 3 days (72 hours). Manufactured. Then, evaluation was performed about the non-bonding area between the base material and the pressure-sensitive adhesive layer.

And except that this supporting sheet was used, the composite sheet for protective film formation was produced and evaluated in the same manner as in the case of Example 1.

Table 1 shows the results.

[Example 3]

In the case of Example 1, the supporting sheet was prepared in the same manner as in Example 1, except that the roll-shaped supporting sheet was left still for 1 day (24 hours) in an air atmosphere and under a temperature condition of 60°C. Manufactured. Then, evaluation was performed about the non-bonding area between the base material and the pressure-sensitive adhesive layer.

And except that this supporting sheet was used, the composite sheet for protective film formation was produced and evaluated in the same manner as in the case of Example 1.

Table 1 shows the results.

[Comparative Example 1]

In the case of Example 1, the support sheet was prepared in the same manner as in Example 1, except that the roll-shaped support sheet was left still for 1 day (24 hours) in an air atmosphere and at a temperature of 50°C. Manufactured. Then, evaluation was performed about the non-bonding area between the base material and the pressure-sensitive adhesive layer.

And except that this supporting sheet was used, the composite sheet for protective film formation was produced and evaluated in the same manner as in the case of Example 1.

Table 1 shows the results.

[Comparative Example 2]

In the case of Example 1, the roll-shaped support sheet wound up was immediately evaluated for a non-bonding region between the substrate and the pressure-sensitive adhesive layer.

And except that this supporting sheet was used, the composite sheet for protective film formation was produced and evaluated in the same manner as in the case of Example 1.

Table 1 shows the results.

[Comparative Example 3]

In the case of Example 1, the roll-shaped support sheet wound up was immediately evaluated for a non-bonding region between the substrate and the pressure-sensitive adhesive layer. In addition, this support sheet was used in the production of the following composite sheet for forming a protective film.

In addition, a protective film-forming film was prepared in the same manner as in Example 1, and a composite sheet for forming a protective film was prepared in the same manner as in Example 1, except that the process of heating and pressing (heat lamination) was not performed. And evaluated.

Table 1 shows the results.

In addition, except for using such a supporting sheet, a composite sheet for forming a protective film was produced and evaluated in the same manner as in the case of Example 1.

Table 1 shows the results.

As is clear from the above results, in Examples 1 to 3, the number of non-bonded regions between the substrate and the pressure-sensitive adhesive layer is 5 or less, and the maximum value (d1) of the interlayer distance is 0.5 μm or less, and the protective film and the protective film The printing visibility through the supporting sheet of the forming film was excellent, and good adhesion between the substrate and the pressure-sensitive adhesive was also good.

In contrast, in Comparative Example 1, the number of non-bonded regions between the substrate and the pressure-sensitive adhesive layer was 5 or less, but the maximum value (d1) of the interlayer distance exceeded 0.5 µm (0.52 µm), and Comparative Examples 2 to 3 In the case, the number of non-bonded areas between the substrate and the pressure-sensitive adhesive layer is 6 or more (8 to 10), and the maximum value (d1) of the interlayer distance exceeds 0.5 μm (0.52 to 0.9 μm), all of which are the substrate and the pressure-sensitive adhesive. The adhesion between them was not sufficient. Further, the printing visibility through the protective film and the support sheet of the film for forming a protective film was also poor.

The present invention can be used to manufacture a semiconductor device.

1A, 1B, 1C... Composite sheet for forming a protective film, 10... Support sheet, 10a... Film side surface (first surface) for forming a protective film of the supporting sheet, 11... Substrate, 11a... The side of the pressure-sensitive adhesive layer of the substrate (the first surface, the uneven surface), 12... Adhesive layer, 12a... The side opposite to the substrate side of the pressure-sensitive adhesive layer (first side), 12b... Side of the substrate side (the second side) of the pressure-sensitive adhesive layer, 13, 23... Film for forming a protective film, 13b... The side of the pressure-sensitive adhesive layer (second surface) of the film for forming a protective film, d ₁ . The maximum value of the interlayer distance between the substrate layer and the pressure-sensitive adhesive layer, T _a ... The thickness of the pressure-sensitive adhesive layer, T _a1 . Minimum value of the thickness of the pressure-sensitive adhesive layer, T _a2 . Maximum value of the thickness of the adhesive layer

Claims (8)

As a support sheet having a substrate and having an adhesive layer on the substrate,
The pressure-sensitive adhesive layer side surface of the substrate is an uneven surface,
A support sheet having a maximum value (d1) of the interlayer distance (d1) between the substrate and the pressure-sensitive adhesive layer is 0.5 μm or less when a test piece is cut out from five places of the support sheet, and the cross section of the pressure-sensitive adhesive layer is observed in these five test pieces. . The method of claim 1,
The support sheet in which the pressure-sensitive adhesive layer is in direct contact with the uneven surface of the substrate. The method according to claim 1 or 2,
A test piece was cut out from five places of the support sheet, and in these five test pieces, when the cross-section of the pressure-sensitive adhesive layer was observed, the number of regions in which the substrate and the pressure-sensitive adhesive layer are not bonded is in the test piece. When observed from an area of 1 mm in the center of the cross section of the test piece in the width direction, the total number of each test piece is 5 or less. A step of preparing a first laminated sheet comprising a substrate, an adhesive layer, and a first release film in this order, and the pressure-sensitive adhesive layer side surface of the substrate is an uneven surface,
The method for producing the support sheet according to any one of claims 1 to 3, comprising a step of storing the first laminated sheet at 53 to 75°C for 24 to 720 hours. A composite sheet for forming a protective film, comprising a film for forming a protective film on the pressure-sensitive adhesive layer in the support sheet according to any one of claims 1 to 3. A substrate, an adhesive layer, and a first release film are provided in this order, and a first laminated sheet having an uneven surface on the side of the pressure-sensitive adhesive layer of the substrate, a third release film, a film for forming a protective film, and a second release film are provided in this order. The process of preparing a laminated film provided with,
A step of storing the first laminated sheet at 53 to 75°C for 24 to 720 hours,
The first release film and the second release film are removed, and the exposed surface of the pressure-sensitive adhesive layer and the exposed surface of the protective film-forming film are bonded to each other, and the substrate, the pressure-sensitive adhesive layer, the protective film-forming film, and the third peeling The process of manufacturing a 2nd laminated sheet provided with a film in this order, and
The method for producing a composite sheet for forming a protective film according to claim 5, comprising the step of storing the second laminated sheet at 53 to 75°C for 24 to 720 hours. The method of claim 6,
The process of bonding the exposed surface of the pressure-sensitive adhesive layer with the exposed surface of the protective film-forming film is performed while pressing at 53 to 75°C with a pressure of 0.3 to 0.8 MPa. The method according to claim 6 or 7,
The first laminated sheet, the laminated film, and the second laminated sheet are each a long laminated sheet or a laminated film, and the first laminated sheet and the second laminated sheet are each in a roll shape in the preserving process. A manufacturing method that is wound and preserved.

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