TW202003739A - Supporting sheet and method of manufacturing the same, and composite sheet for forming protective film and method of manufacturing the same - Google Patents

Abstract

A supporting sheet of the present invention includes a substrate and an adhesive layer on the substrate, wherein the surface of the adhesive layer side of the substrate is an uneven surface. When test pieces are cut from five locations on the supporting sheet and the cross-sections of the adhesive layers of the five test pieces are observed, the maximum value (d1) of the interlayer distance between the substrate and the adhesive layer is 0.5 μm or less. A composite sheet for forming prtective film is equipped with a film for forming protective film on the adhesive layer of the supporting sheet.

Description

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

The present invention relates to a support 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 have been manufactured using the so-called "face down" mounting method. The inverted method uses a semiconductor wafer provided with electrodes such as bumps on the circuit surface, and the electrodes are bonded to the substrate by the electrodes. Therefore, the opposite surface of one side of the semiconductor wafer on which the circuit surface is provided is exposed.

An organic material-containing resin film used as a protective film is formed on the back surface of the exposed semiconductor wafer, and then assembled into a semiconductor device in the form of a semiconductor wafer with a protective film. The protective film is used to prevent cracks in the semiconductor wafer after the dicing step and packaging.

Such a protective film is formed by, for example, curing a thin film for forming a curable protective film. In addition, the film for forming a non-curable protective film whose physical properties are adjusted can also be directly used as a protective film. Therefore, the thin film for forming a protective film is used for attaching to the back surface of a semiconductor wafer. For example, the protective film forming film may be attached to the back surface of the semiconductor wafer in the state of a protective film forming composite sheet integrated with the support sheet used for processing the semiconductor wafer, or may not be integrated with the support sheet It is attached to the back of the semiconductor wafer in the chemical state.

After the protective film forming composite sheet is attached to the back surface of the semiconductor wafer by using the protective film forming film, it can be implemented according to the respective appropriate timing. For example, the protective film is formed by hardening the protective film forming film, the protective film forming film or The cutting of the protective film, the singulation (dicing) of the semiconductor wafer into a semiconductor wafer, and the picking up of the semiconductor wafer with the protective film forming film or protective film on the back side (the semiconductor wafer or film with protective film forming film) Semiconductor film of protective film) etc. On the other hand, when picking up a semiconductor wafer with a thin film for forming a protective film, the semiconductor film with a protective film is formed by hardening the thin film for forming a protective film, and finally a semiconductor device is manufactured using the semiconductor wafer with a protective film. Accordingly, the support sheet in the composite sheet for forming a protective film can be used as a dicing sheet. In addition, when the thin film for forming a protective film is non-curable, the thin film for forming a protective film is directly used as a protective film in these steps.

On the other hand, after the film for protective film formation is attached to the back surface of the semiconductor wafer without being integrated with the support sheet, the double side of the film for protective film formation is opposite the surface to which the semiconductor wafer is attached Attach the support sheet to the exposed surface. For the rest, the semiconductor wafer with a protective film or the semiconductor wafer with a thin film for forming a protective film is obtained according to the same method as in the case where the composite film for forming a protective film is used, and a semiconductor device is manufactured. In this case, the film for forming a protective film is attached to the back surface of the semiconductor wafer in a state where it is not integrated with the support sheet, but by integrating with the support sheet after attachment, a composite sheet for forming a protective film is formed .

For such a composite film for forming a protective film, for example, there is disclosed a dicing tape integrated type semiconductor backside protective film, which is a dicing tape including a dicing tape (support sheet) and a semiconductor backside protective film (protective film forming film) A thin film for protecting the back surface of a bulk semiconductor (a composite sheet for forming a protective film), and the dicing tape (support sheet) has a base material having a rough surface and an adhesive layer stacked on the rough surface of the base material The film for semiconductor back surface protection (film for forming a protective film) is laminated on the adhesive layer of the dicing tape; wherein the haze of the dicing tape is 45% or less (refer to Patent Document 1).

However, the composite sheet for forming a protective film (a dicing tape-integrated semiconductor backside protection film) disclosed in Patent Document 1 has an adhesive layer stacked on the uneven surface of the substrate, so there is an adhesive that cannot fully track the substrate. The unevenness of the material leads to the unbonded areas (non-bonded areas) between the substrate and the adhesive. In addition, printing may be performed on one surface of the adhesive layer of the protective film or the film for forming a protective film by laser irradiation, but depending on the uneven shape of the adhesive layer, it may cause the substrate and the adhesive to separate The visibility of the layer marking is reduced. [Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5432853

(Problems to be solved by the invention)

An object of the present invention is to provide a support sheet and a composite sheet for forming a protective film including the above support sheet, a support sheet composed of an adhesive layer on an uneven surface of a base material, and a protection film for forming a protective film on the adhesive layer In the composite sheet for film formation, good adhesion between the base material and the adhesive, and good marking visibility of the protective film or the film for forming a protective film can be achieved. (Technical means to solve the problem)

The present invention includes the following aspects. [1] A support sheet comprising a base material, and a support sheet provided with an adhesive layer on the base material, wherein the base material has a concave-convex surface on one surface of the adhesive layer, from the support sheet 5 When the test pieces were cut out from each place and the cross-section of the adhesive layer was observed with respect to these five test pieces, the maximum value (d1) of the interlayer distance between the base material and the adhesive layer was 0.5 μm or less. [2] The support sheet according to [1] above, wherein the adhesive layer directly contacts the uneven surface of the base material. [3] The support sheet according to the above [1] or [2], wherein the test piece is cut out from 5 places of the support sheet, and the cross section of the adhesive layer is observed with respect to these 5 test pieces, the base material The number of unattached areas to the adhesive layer was observed when the test piece was observed in a 1 mm area at the center of the cross-sectional width direction of the test piece, and the total number of each test piece was 5 or less. [4] A method for manufacturing a support sheet is the method for manufacturing a support sheet described in any one of the above [1] to [3], including the following steps: Preparing a first laminated sheet including a substrate, an adhesive layer, and a first release film in sequence, and the substrate has a concave-convex surface on one surface of the adhesive layer; and The first laminated sheet is stored at 53 to 75°C for 24 to 720 hours.

[5] A composite sheet for forming a protective film, which is provided with a thin film for forming a protective film on the adhesive layer in the support sheet described in any one of the above [1] to [3]. [6] A method for manufacturing a composite sheet for forming a protective film is the method for manufacturing a composite sheet for forming a protective film as described in [5] above, which includes the following steps: Prepare a first laminate sheet and a laminate film, the laminate film includes a third release film, a protective film forming film, and a second release film. The first laminate sheet includes a substrate, an adhesive layer, and a first release film in sequence, And the base material is a concave-convex surface by one surface of the adhesive layer; Store the first laminated sheet at 53~75℃ for 24~720 hours; The first peeling film and the second peeling film are removed, and the exposed surface of the adhesive layer is bonded to the exposed surface of the protective film forming film, and the manufacturing sequence includes the substrate, the adhesive layer, and the protective film Forming film and the second lamination sheet of the above-mentioned third release film; and The above second laminated sheet is stored at 53 to 75°C for 24 to 720 hours. [7] The method for manufacturing a composite sheet for forming a protective film as described in [6] above, wherein the step of bonding the exposed surface of the adhesive layer to the exposed surface of the protective film forming film is 53 At ~75°C, press with 0.3~0.8MPa pressure. [8] The manufacturing method according to the above [6] or [7], wherein the first laminate sheet, the laminate film and the second laminate sheet are each a long laminate sheet or a laminate film; the first laminate The sheet and the second laminated sheet are respectively wound and stored in a roll shape in the storing step. [Effect of the invention]

By forming the composite sheet for forming a protective film using the support sheet of the present invention, good adhesion between the base material and the adhesive, and good marking visibility of the protective film or the film for forming a protective film across the support sheet can be achieved.

◇Composite sheet for forming support sheet and protective film A support sheet according to an embodiment of the present invention is a support sheet including a base material and an adhesive layer provided on the base material; wherein the base material has a concave-convex surface on one surface of the adhesive layer; from the support sheet 5 When the test pieces were cut out from each place and the cross-section of the adhesive layer was observed for these five test pieces, the maximum interlayer distance (also referred to as "d1" in this specification) between the substrate and the adhesive layer was 0.5 μm or less.

By the maximum value (d1) of the interlayer distance between the substrate and the adhesive layer being 0.5 μm or less, good adhesion between the substrate and the adhesive, and a good protective film or film for forming a protective film across the support sheet can be achieved Imprint visibility.

A support sheet according to an embodiment of the present invention is a support sheet including a base material and an adhesive layer provided on the base material; wherein the base material has a concave-convex surface on one surface of the adhesive layer; from the support sheet 5 Cut the test piece at each place, and for these 5 test pieces, when the minimum and maximum thickness of the adhesive layer are obtained, it is better to be the average of the above minimum value (also referred to as "S value" in this manual). 1.5 μm or more, and the average value of the above-mentioned maximum value (also referred to as “L value” in this specification) is 9 μm or less. Furthermore, when the test piece is cut out from 5 places of the above-mentioned support sheet, and the cross-section of the adhesive layer is observed for these 5 test pieces, it is preferable that the number of unbonded areas between the base material and the adhesive layer is 5 or less . Furthermore, in the composite sheet for forming a protective film according to an embodiment of the present invention, a film for forming a protective film is provided on the adhesive layer in the support sheet.

Furthermore, when the S value of the adhesive layer is 1.5 μm or more, the lamination property between the adhesive layer and the film for forming a protective film tends to be good. The term "stackability" in this manual refers to the normality of the stacking state of the target 2 layers unless otherwise stated. The “good stackability” means, for example, that there are no unbonded areas (voids) between two adjacent layers of the object, or that the number of unbonded areas is small and the interlayer distance of the unbonded areas is small. On the other hand, when the L value of the adhesive layer is 9 μm or less, the visibility of the engraving of the protective film or the film for forming a protective film via the support sheet is likely to be good.

The above test piece was obtained by cutting out the support piece at five places, and cutting the support piece in its entire thickness direction. The test piece system includes small pieces constituting all layers of the support piece.

The size of the test piece is not particularly limited, and it is preferable that the length of one side of the accumulated surface or exposed surface constituting each layer (base material, adhesive layer, etc.) of the test piece be 2 mm or more. By using test pieces of this size, the S value and L value of the adhesive layer can be obtained with higher accuracy. The maximum value of the length of one side is not particularly limited. For example, from the viewpoint of making the test piece easier, the length of the one side is preferably 10 mm or less.

The plane shape of the test piece-that is, the shape of the accumulated surface or exposed surface constituting each layer (base material, adhesive layer, etc.) of the test piece, preferably a polygonal shape, from the viewpoint of easier cutting from the test piece, more preferably a quadrilateral shape.

The test piece preferably includes, for example, a quadrilateral shape having a size of 3 mm×3 mm in which the accumulated surface or exposed surface of each layer (base material, adhesive layer, etc.) constituting the test piece is formed. However, this is just one example of a better test piece.

The cutting position of the support sheet at 5 places of the test piece is not particularly limited. In order to obtain the S value and L value of the adhesive layer with higher accuracy, the predetermined position of the lamination of the protective film forming film described later can be considered. select. For example, at a predetermined position for laminating a thin film for forming a protective film, the supporting sheet is selected to be a place that belongs to the center (center of gravity) of the thin film for forming a protective film and that is close to the periphery of the thin film for forming a protective film In this center (center of gravity) part, 5 places such as 4 predetermined places are arranged almost in point symmetry.

In the support piece, the distance between the centers (gravity centers) of the test piece cutting positions is preferably 50 to 200 mm. With this setting, the S value and L value of the adhesive layer can be obtained with higher accuracy.

In order to obtain the S value and L value of the adhesive layer from the test piece, the cross section is formed again for the test piece, and then for the formed cross section, the minimum and maximum thickness of the adhesive layer can be measured on each test piece one by one . The reconstructed cross-section may have only one side or more than two sides for one test piece, but usually only one side is sufficient. Then, from these at least 5 minimum and maximum values, the S and L values can be calculated.

The test piece system can form a cross section according to a known method. For example, by using a well-known cross-section sample production device (cross-section polishing machine), it is possible to suppress variations and achieve high reproducibility, and to form a cross-section in a test piece.

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

In the above-mentioned cross section of each test piece, the area of the maximum value (d1) of the interlayer distance between the base material and the adhesive layer is measured so as to be orthogonal to the direction in which the layers constituting the test piece (base material, adhesive layer, etc.) are stacked (roughly opposite It is preferably in the region of 50 to 1500 μm in each layered layer or parallel direction of the exposed surface). With this setting, the maximum value (d1) of the interlayer distance between the substrate and the adhesive layer can be measured with high efficiency and high accuracy. The determination of the minimum and maximum thickness of the adhesive layer is the same.

When the minimum thickness of the adhesive layer is compared between the support sheet that has not yet formed the composite sheet for forming a protective film and the support sheet that has already formed the composite sheet for forming a protective film, the minimum values are the same as each other or have been constructed The minimum value of the support sheet of the composite sheet for forming a protective film is slightly smaller. In such a small case, the difference is negligible. The same applies to the maximum thickness of the adhesive layer. That is, when the maximum thickness of the adhesive layer is compared between the support sheet that has not yet constituted the composite sheet for forming a protective film and the support sheet that has already constituted the composite sheet for forming a protective film, the maximum values are the same as each other, or The above-mentioned maximum value of the support sheet that has constituted the composite sheet for forming a protective film is slightly smaller. In such a small case, the difference is negligible. Therefore, instead of using a support sheet, a test piece cut from a composite sheet for forming a protective film can be used, and the maximum value (d1) of the interlayer distance can also be obtained according to the same method as when the test piece cut out from the support sheet is used. Take the S and L values of the adhesive layer. When the test piece cut out from the composite film for protective film formation is used in this way, if the maximum interlayer distance (d1) is 0.5 μm or less, the composite film for protective film formation 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 in which a thin film for forming a protective film is provided on the adhesive layer in the support sheet; The test piece was cut out at 5 places of the piece, and the cross-section of the adhesive layer was observed for these 5 test pieces, and the maximum value (d1) of the interlayer distance between the base material and the adhesive layer was 0.5 μm or less.

Similarly, instead of using a support sheet that has not yet constituted a composite sheet for forming a protective film, a test piece cut out from the composite sheet for forming a protective film may be used. In the same way as when the test piece cut out from the support sheet is used, adhesion S value and L value of the agent layer. Accordingly, when using a test piece cut out from the composite film for forming a protective film, if the S value of the adhesive layer is 1.5 μm or more and the L value of the adhesive layer is 9 μm or less, the composite film for forming a protective film is easy The above-mentioned effects of the present invention are reflected.

That is, the composite sheet for forming a protective film according to an embodiment of the present invention is preferably a composite sheet for forming a protective film provided with a thin film for forming a protective film on the adhesive layer in the support sheet; When the test piece was cut at 5 places of the composite sheet for forming, and the minimum and maximum values of the thickness of the adhesive layer were obtained for these 5 test pieces, the average value (S value) of the above minimum value reached 1.5 μm or more, and The average value (L value) of the maximum value is 9 μm or less.

In addition, the test piece cut out from the composite film for protective film formation was obtained by cutting the entire composite film for protective film formation in the thickness direction, and was a small piece including all layers constituting the composite film for protective film formation.

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. In addition, the drawings used in the following description are for the sake of easy understanding of the characteristics of the present invention, and for the sake of convenience, the important parts are partially enlarged and illustrated, and the dimensional ratios of the components and the like are not necessarily the same as the actual sizes.

FIG. 1 is a schematic cross-sectional view of a composite sheet for forming a support sheet and a protective film according to an embodiment of the present invention. The composite sheet 1A for forming a protective film shown here includes a base material 11, an adhesive layer 12 is provided on the base material 11, and a thin film 13 for forming a protective film is provided on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, and the composite sheet 1A for forming a protective film, in other words, is provided on one side of the support sheet 10 (also referred to as "the first side" in this specification) 10a for protection The structure of the thin film 13 for film formation. In addition, the composite sheet 1A for forming a protective film further includes a release film 15 on the film 13 for forming a protective film.

In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one side of the base material 11 (also referred to as "first surface" in this specification) 11a, and the surface of the adhesive layer 12 opposite to the base material 11 side (Also referred to as the "first surface" in this specification) The entire surface of 12a is laminated with a thin film 13 for forming a protective film, in the thin film 13 for forming a protective film, the surface opposite to the adhesive layer 12 side (also referred to as "in this specification" The first surface") part of 13a (that is, the area near the peripheral edge), the adhesive layer 16 for the jig is laminated, and one surface of the adhesive layer 16 for the jig is not laminated on the first surface 13a of the protective film forming film 13; Without contacting the adhesive layer 16 for the jig with one surface 16a (upper surface and side surface) of the protective film forming film 13, the peeling film 15 is laminated. In addition, in FIG. 1, the element symbol 13b represents a surface of the protective film forming film 13 that faces the adhesive layer 12 (also referred to as "second surface" in this specification).

The adhesive layer 16 for a jig may have, for example, a single-layer structure containing an adhesive component, or a layer containing an adhesive component may be laminated on both sides of a sheet material to be a core material to form a multiple-layer structure.

In the composite sheet 1A for forming a protective film, the first surface 11a of the base material 11 is an uneven surface. In addition, the adhesive layer 12 is provided in direct contact with the first surface (concavo-convex surface) 11a of the base material 11. Therefore, the adhesive layer 12 faces the surface 11 of the substrate 11 (also referred to as "second surface" in this specification) 12b as an uneven surface.

In the composite sheet 1A for forming a protective film, the surface of the substrate 11 opposite to the adhesive layer 12 side (also referred to as "second surface" in this specification) 11b may be an uneven surface or a smooth surface (non-concave surface, Glossy surface), but smooth surface is preferred. The second surface 11b of the base material 11 can also be referred to as a surface (also referred to as a "second surface" in this specification) 10b of the support sheet 10 on the side opposite to the protective film forming film 13 side. The "concave-convex surface" and "smooth surface" will be described in detail later.

The composite sheet 1A for forming a protective film shown in FIG. 1 is in a state where the peeling film 15 has been removed, and the back surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film. On the surface 16a of the adhesive layer 16, a jig such as a ring frame is attached to the upper surface and used.

2 is a schematic cross-sectional view showing a composite sheet for forming a protective film and a support sheet according to another embodiment of the present invention. In addition, in the subsequent drawings of FIG. 2, the same constituent elements as those shown in the previously described drawings are given the same reference numerals as those in the previously described drawings, and detailed descriptions are omitted.

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

In the composite sheet 1B for forming a protective film, the first surface 11a of the base material 11 also belongs to the uneven surface. In addition, the adhesive layer 12 is provided in direct contact with the first surface (concavo-convex surface) 11a of the base material 11. Therefore, one surface (second surface) 12b of the adhesive layer 12 facing the substrate 11 is an uneven surface. In the composite sheet 1B for forming a protective film, the second surface 11b of the base material 11 (in other words, the second surface 10b of the support sheet 10) may be either a concave-convex surface or a smooth surface (non-concavo-convex surface), but A smooth surface is better.

The composite sheet 1B for forming a protective film shown in FIG. 2 is in a state where the peeling film 15 has been removed, and a semiconductor wafer is attached to a part of the central side of the first surface 13a of the film 13 for forming a protective film (not (Illustrated), it is used by attaching a jig such as a ring frame to the area near the periphery.

3 is a schematic cross-sectional view of a composite sheet for forming a protective film and a support sheet according to still another embodiment of the present invention. The composite sheet 1C for protective film formation shown here is the same as the composite sheet 1B for protective film formation shown in FIG. 2 except that the shape of the thin film for protective film formation is different. That is, the composite sheet 1C for forming a protective film includes a base material 11, an adhesive layer 12 is provided on the base material 11, and a thin film 23 for forming a protective film is further provided on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, and the protective film forming composite sheet 1C, in other words, is provided on the first surface of the support sheet 10 (on the side of the protective film forming film 23) 10a, and is laminated The configuration of the thin film 23 for forming a protective film. In addition, the composite sheet 1C for forming a protective film further includes a peeling film 15 on the film 23 for forming a protective film.

In the composite sheet 1C for forming a protective film, an adhesive layer 12 is laminated on the first surface 11a of the base material 11, and a protective film forming layer is laminated on a part of the first surface 12a of the adhesive layer 12 (that is, the central region)膜23。 The film 23. In addition, on the first surface 12 a of the adhesive layer 12, the area where the protective film forming film 23 is not laminated, and the protective film forming film 23 is not in contact with the surface 23 a (upper and side surfaces) of the adhesive layer 12, are laminated The film 15 is peeled off. In addition, in FIG. 3, the element symbol 23b represents a surface of the protective film forming film 23 that faces the adhesive layer 12 (also referred to as "second surface" in this specification).

When the protective film forming composite sheet 1C is viewed from above, the surface area of the protective film forming film 23 is smaller than the surface area of the adhesive layer 12 and has a shape such as a circular shape.

In the composite sheet 1C for forming a protective film, the first surface 11a of the base material 11 also has an uneven surface. In addition, the adhesive layer 12 is provided in direct contact with the first surface (concavo-convex surface) 11a of the base material 11. Therefore, one surface (second surface) 12b of the adhesive layer 12 facing the substrate 11 is an uneven surface. In the composite sheet 1C for forming a protective film, the second surface 11b of the base material 11 (in other words, the second surface 10b of the support sheet 10) may be either a concave-convex surface or a smooth surface (non-concavo-convex surface), But smooth surface is better.

The composite sheet 1C for forming a protective film shown in FIG. 3 is in a state where the peeling film 15 has been removed, and the back surface of a semiconductor wafer (not shown) is attached to the surface 23a of the film 23 for forming a protective film, and furthermore, the adhesive layer 12 In the area of the first surface 12a where the protective film forming film 23 is not laminated, a jig such as a ring frame is attached and used.

In addition, in the composite sheet 1C for forming a protective film shown in FIG. 3, the adhesive for jigs as shown in FIG. 1 may be stacked on the first surface 12a of the adhesive layer 12 where the protective film forming film 23 is not stacked. Layer (not shown). Such a composite sheet 1C for forming a protective film having an adhesive layer for a jig is used in the same manner as the composite sheet for forming a protective film shown in FIG. 1 by attaching a jig such as a ring frame on the adhesive layer for a jig.

Accordingly, the composite sheet for forming a protective film can include an adhesive layer for jigs regardless of the form of the support sheet and the film for forming a protective film. However, in general, as shown in FIG. 1, it is preferable that a composite sheet for forming a protective film including an adhesive layer for a jig is provided with an adhesive layer for a jig 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 that shown in FIGS. 1 to 3, and a part of the parts shown in FIGS. 1 to 3 may be changed or deleted within the scope of not damaging the effects of the present invention. As for the configuration, other configurations may be further added to the configurations 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 provided between the base material 11 and the adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by laminating in the thickness direction in the order of the base material, the intermediate layer, and the adhesive layer. The middle layer system can be arbitrarily selected according to the purpose. In addition, the composite sheet for forming a protective film shown in FIGS. 1 to 3 may be provided with a layer other than the intermediate layer at any place. Furthermore, in the composite sheet for forming a protective film, a gap may be locally generated between the peeling film and the layer directly in contact with the peeling film. In addition, the size, shape, etc. of each layer of the composite sheet for forming a protective film 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, it is preferable that the adhesive layer directly contacts the uneven surface (first surface) of the substrate, in other words, between the substrate and the adhesive layer No intermediate layer is provided, but an adhesive layer is laminated directly on the substrate. Furthermore, in the composite sheet for forming a protective film, it is preferable that the film for forming a protective film directly contacts the first surface of the adhesive layer. In other words, no other layer is provided between the adhesive layer and the film for forming a protective film. Instead, a thin film for forming a protective film is directly contacted on the adhesive layer. Furthermore, the composite sheet for forming a protective film preferably satisfies all these conditions, that is, it is constituted by directly contacting and laminating each other in the thickness direction in the order of the substrate, the adhesive layer, and the film for forming a protective film.

The support sheet is preferably transparent. The supporting sheet can also be colored for other purposes, or it can be vapor-deposited with other layers. For example, when the energy ray of the thin film for protective film formation is hardenable, it is preferable that the support sheet penetrate the energy ray.

In this specification, the "energy rays" refer to electromagnetic waves or charged particle beams having energy quanta, and examples include ultraviolet rays, radiation, and electron beams. The ultraviolet system can be irradiated using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black-light lamp or an LED lamp of an ultraviolet source. The electron beam system can irradiate a generator generated by an electron beam accelerator or the like. In this specification, the "energy ray curability" refers to the property of being hardened by irradiation of energy rays; the so-called "non-energy ray curability" is the property of not being hardened even if energy rays are irradiated.

The light transmittance of the support sheet at a wavelength of 375 nm is preferably at least 30%, more preferably at least 50%, and particularly good at more than 70%. When the light transmittance in this range is within this range, when the protective film forming film is irradiated with energy rays (ultraviolet rays) through the support sheet, the hardening degree of the protective film forming film is further improved. The upper limit of the transmittance of the light at a wavelength of 375 nm of the support sheet is not particularly limited. For example, the light transmittance is preferably 95% or less.

The light transmittance of the support sheet at a wavelength of 532 nm is preferably at least 30%, more preferably at least 50%, and particularly preferably at least 70%. With the above-mentioned light transmittance within this range, when the protective film forming film or protective film is irradiated with laser light through the support sheet, it can be marked more clearly. The upper limit value of the transmittance of light of the support sheet at a wavelength of 532 nm is not particularly limited. For example, the above light transmittance is preferably 95% or less.

The light transmittance of the support sheet at a wavelength of 1064 nm is preferably at least 30%, more preferably at least 50%, and particularly good at more than 70%. With the above-mentioned light transmittance within this range, when the protective film forming film or protective film is irradiated with laser light through the support sheet, it can be marked more clearly. The upper limit value of the light transmittance of the wavelength of 1064 nm of the support sheet is not particularly limited. For example, the light transmittance is preferably 95% or less.

The penetration clarity of the support sheet is preferably 30 or more, more preferably 100 or more, and especially 200 or more. With the above-mentioned penetration clarity within such a range, it is easier to confirm the lifting and falling of the protective film forming film, defective printing, and defects through the support sheet. The penetration clarity of the support sheet is not particularly limited. For example, the above-mentioned penetration clarity may be below 430. The penetration clarity of the support sheet can be measured according to JIS K 7374-2007.

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

○Base material The above-mentioned base material is in the form of a sheet or a film, and has an uneven surface.

In this specification, the "concavo-convex surface" refers to a surface having a maximum height roughness Rz of 0.01 μm or more specified in accordance with JIS B 0601:2013. Furthermore, the so-called "smooth surface" refers to a surface that is not uneven, but a high-smoothness surface, also known as a "non-concave surface" or "shiny surface". For example, a smooth surface includes a surface having extremely small unevenness that does not belong to the above-mentioned uneven surface.

The base material may have only one of the surfaces being uneven, or both sides may have uneven surfaces, and it is preferred that only one of the surfaces be uneven. In other words, it is preferable that only one of the substrates is a smooth surface. In the support sheet, the uneven surface of the base material becomes one surface on the side where the adhesive layer is provided.

The substrate system may be composed of only one layer (single layer), or may be composed of more than two plural layers. When composed of plural layers, these plural layer systems may be the same as or different from each other. The combination is not particularly limited. When the base material is composed of a plurality of layers, among the plurality of layers, one of the outermost layers (the side closest to the adhesive layer, or the two sides closest to the adhesive layer and the side farthest from the two sides) becomes the above-mentioned irregularities surface.

This specification is not limited to the case of the substrate. The so-called "multiple layer systems may be the same or different from each other" means "all layers may be the same, all layers may be different, or only some of the layers may be the same" ; Also, the so-called "multiple layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other."

The maximum height roughness (Rz) measured according to JIS B 0601:2013 on the uneven surface (first surface) on which the adhesive layer is provided on one side of the substrate is preferably 0.01 to 8 μm and more preferably 0.1 to 7 μm , The special good line is 0.5~6μm. By the Rz of the base material being equal to or higher than the lower limit value, it is possible to suppress the occurrence of defects when the base material is wound into a roll shape alone and unwound. In addition, in the manufacturing process of the support sheet or the composite sheet for forming a protective film, the laminate containing the base material is similarly prevented from causing defects during winding and unwinding. On the other hand, when the Rz of the base material is below the upper limit value, the lamination of the adhesive layer and the film for forming a protective film and the marking inspection of the protective film or the film for forming a protective film through the support sheet can be performed Sex is better.

When both sides of the base material are uneven surfaces, the unevenness of the two sides may be the same or different.

Examples of the constituent material system of the base material include various resins. Examples of the above resin system include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, and polymethylmethacrylate Polyolefins other than polyethylene such as amylpentene and norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-norbornene Vinyl copolymers such as copolymers (copolymers obtained by using ethylene in a single system); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained by using vinyl chloride in a single system); polystyrene; Polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalene dicarboxylate Polyesters such as esters, wholly aromatic polyesters having an aromatic ring group in all constituent units; copolymers of two or more of the above polyesters; poly(meth)acrylates; polyurethanes; polyurethane acrylates; polyimides Polyamide; Polycarbonate; Fluorine resin; Polyacetal; Modified polyphenylene ether; Polyphenylene sulfide; Polyphenolic; Polyether ketone, etc. In addition, the resin may also be a polymer alloy such as a mixture of the polyester and the resin outside. The polymer blend of the above-mentioned polyester and the resin outside thereof is preferably a relatively small amount of resin other than polyester. In addition, the above-mentioned resin may also be exemplified by a cross-linked resin cross-linked after one or more of the above-mentioned resins exemplified so far; one or more of the above-mentioned resins exemplified so far are used Modified resins such as ionic polymers.

In this specification, the term "(meth)acrylic acid" includes the concepts of both "acrylic acid" and "methacrylic acid". Similar terms for (meth)acrylic acid are also the same. For example, the so-called "(meth)acryloyl" includes the concepts of both "acryloyl" and "methacryloyl"; the so-called "(meth)acrylic" "Ester" includes the concepts of both "acrylate" and "methacrylate".

The resin system constituting the base material may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio system may 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 base material is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer can be further improved. As described above, since the base material has an uneven surface, its thickness varies depending on the position of the base material. Therefore, the minimum value of the thickness of the substrate can be above the above lower limit, and the maximum value of the thickness of the substrate can be below the above upper limit. In addition, the "base material thickness" refers to the thickness of the entire base material, for example, the thickness of the base material composed of a plurality of layers, refers to the total thickness of all layers constituting the base material.

The thickness of the base material can be measured by observing the side surface or cross section of the base material using, for example, a scanning electron microscope (SEM). The cross section of the base material can be formed, for example, in the same manner as the cross section of the test piece of the above-mentioned composite sheet for forming a support sheet and a protective film.

For example, in the same manner as the method described above, the test piece is cut from a plurality of places (for example, 5 places) of the support sheet or the protective film forming composite sheet, and the minimum and maximum thickness of the base material are obtained for this test piece. When these minimum and maximum average values are further obtained from these values, the minimum average value may be greater than the lower limit of the thickness of the substrate, and the average maximum value may also be the upper limit of the thickness of the substrate Below the value.

The base material may contain various well-known additives such as fillers, colorants, antistatic agents, antioxidants, organic slip agents, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the above resins.

The substrate is preferably transparent. The base material may be colored according to the purpose, and may be vapor-deposited with other layers. For example, when the thin film for forming a protective film is energy-ray curable, it is preferable that the base material penetrate the energy line.

In order to improve the adhesion of the layer directly in contact with the adhesive layer and the like provided on the substrate, the surface can also be subjected to corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone and ultraviolet irradiation treatment, for example , Flame treatment, chromic acid treatment, hot air treatment and other oxidation treatment and so on. Furthermore, the surface of the substrate can also be treated with primer. Furthermore, the substrate system may have an antistatic coating; when the composite sheet for forming a protective film is stacked and stored, it may have a layer that prevents the substrate from adhering to other sheets, the substrate from adhering to a platform, and the like.

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

When a base material having no uneven surface (in other words, a base material having smooth surfaces on both sides) is used, the smooth surface of the base material may be subjected to uneven processing. The unevenness treatment can be carried out according to a known method. For example, by using a metal roll or metal plate with an uneven surface, by pressing the above-mentioned uneven surface against the smooth surface of the base material, the smooth surface of the base material can be subjected to the uneven surface treatment. At this time, it is preferable to press the heated metal roller or metal plate against the smooth surface of the base material. In addition, the smooth surface of the base material may be subjected to roughening treatment by sandblasting or solvent treatment.

○Adhesive layer The adhesive layer is in the form of a sheet or a film. In the adhesive layer, regardless of whether an intermediate layer is provided between the base material and the adhesive layer, it will be affected by the above-mentioned uneven surface of the base material, causing at least one surface adjacent to the base material to become an uneven surface.

The adhesive layer system may be composed of one layer (single layer), or may be composed of more than two layers. When composed of plural layers, these plural layers may be the same or different from each other, and the The combination is not particularly limited. When the adhesive layer is composed of a plurality of layers, one of the outermost layers of the plurality of layers (the surface closest to the substrate) will become the above-mentioned uneven surface.

Here, referring to the drawings, the base material and the adhesive layer will be described in more detail. 4 is a schematic enlarged cross-sectional view of 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, the peeling film is not shown in FIG. 4.

As described above, the first surface 11a of the base material 11 is an uneven surface. The adhesive layer 12 is disposed so as to directly contact the first surface (concavo-convex surface) 11a of the substrate 11, and the second surface 12 b of the adhesive layer 12 can easily follow the first surface 11 a of the substrate 11. Therefore, the second surface 12b of the adhesive layer 12 also has an uneven surface.

The thickness T _a of the adhesive layer 12 is not fixed, and will vary depending on the location of the adhesive layer 12. Here, the minimum thickness of the adhesive layer 12 is represented by the symbol T _a1 , and the maximum thickness of the adhesive layer 12 is represented by the symbol T _a2 .

In the composite sheet 1A for forming a protective film, test pieces were cut out from five places, cross sections were formed in these five test pieces, and the minimum thickness T _a1 and the maximum value T of the adhesive layer were obtained for the newly formed cross sections. _a2 . Then, the average value (the above S value) is obtained from at least 5 T _a1 values, preferably 1.5 μm or more, and the average value (the above L value) is obtained from at least 5 T _a2 values, preferably the value Below 9μm.

From the composite sheet for protective film formation 1A, a test piece, a cross-sectional formation of the test piece, the measurement of the maximum value (d1) of the interlayer distance between the base material and the adhesive layer of the above-mentioned cross section, and the minimum thickness of the adhesive layer T _a1 and the maximum The measurement of the value T _a2 is as described above, and can be carried out in the same manner as when a test piece is cut out from a support sheet that has not yet constituted a composite sheet for forming a protective film.

In addition, the enlarged cross-sectional view of the support sheet that has not yet constituted the composite sheet for forming a protective film is the same as the case where the film 13 for forming a protective film is omitted in FIG. 4.

As the composite sheet 1A for forming a protective film, there is shown between the base material 11 and the adhesive layer 12 that there is a non-bonded area (also referred to as “unbonded area” in this specification) 91. However, even if the protective film forming composite sheet 1A has such an unbonded area 91, the size of the unbonded area 91 in the thickness direction of the protective film forming composite sheet 1A, that is, the maximum value of the interlayer distance between the substrate and the adhesive layer ( d1) The composite sheet 1A for forming a protective film having a thickness of 0.5 μm or less still has good adhesion between the base material 11 and the adhesive layer 12 and good marking visibility of the protective film or the film for forming a protective film via the support sheet.

In addition, in this specification, the "size of the unattached region in the thickness direction of the composite sheet for forming a protective film" refers to "the distance between two adjacent layers in the thickness direction of the sheet in the composite sheet for forming a protective film" , Sometimes referred to as "interlayer distance". For example, the above-mentioned "size of the unattached region 91 in the thickness direction of the composite sheet for protective film formation 1A" means "the interlayer distance between the substrate 11 and the adhesive layer 12 in the thickness direction of the sheet 1A". When the size of the unattached area (interlayer distance) at one place changes, the maximum value is adopted as the size of the unattached area (interlayer distance).

The size of the unlaminated area (interlayer distance) 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 adhesive layer, for example. That is, a cross-section is formed in the test piece of the protective film forming composite sheet according to the same method as when obtaining the R value of the adhesive layer, and then the size of the unlaminated area can be obtained from this cross-section. Alternatively, in the case where no test piece is produced, a cross-section may be formed by the protective film-forming composite sheet itself, and then the size of the unlaminated area may be obtained from this cross-section.

The size of the non-laminated area 91 (the maximum value of the above-mentioned interlayer distance) may be, 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.

In the composite sheet 1A for forming a protective film, there may be no unbonded area 91 at all. In this specification, when the size of the unattached area is more than 0.05 μm, it is considered that there is an unattached area, but when there is no unattached area 91 at all, the size of the unattached area 91 (interlayer distance ) Case of 0 μm.

Here, the composite sheet 1A for protective film formation is taken as an example to describe the base material and the adhesive layer. However, the composite sheet for protective film formation in other embodiments, such as the composite sheet for protective film formation 1B and the composite sheet for protective film formation 1C, etc. In the case of the sheet, the base material and the adhesive layer are also the same.

The S value of the adhesive layer is mentioned before it is not damaged and the effect of the present invention is not particularly limited, and it is preferably 1.5 μm or more and less than 9 μm. A more preferred system is 1.7 μm or more, and a particularly preferred system is 1.9 μm or more. For example, it may be any of 2.3 μm or more, 2.7 μm or more, 3.1 μm or more, and 3.5 μm or more. When the S value is equal to or higher than the lower limit value, the lamination property of the adhesive layer and the thin film for forming a protective film can be improved.

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

The S value of the adhesive layer can be appropriately adjusted within a range set by any combination of the above-described preferred lower limit value and upper limit value. For example, the S value of the adhesive layer is preferably from 1.5 to 8 μm, more preferably from 1.7 to 8 μm, and particularly from 1.9 to 8 μm, for example, any of 2.3 to 8 μm, 2.7 to 8 μm, 3.1 to 8 μm, and 3.5 to 8 μm. One. However, these are only examples of the S value of the adhesive layer.

The L value of the adhesive layer is mentioned before it is not damaged and the effect of the present invention is not particularly limited, and it is preferably 9 μm or less and more than 1.5 μm. A more preferred system is 8.6 μm or less, and a particularly preferred system is 8.3 μm or less. For example, it may be any of 7.7 μm or less, 7.3 μm or less, 6.9 μm or less, and 6.5 μm or less. When the L value is equal to or lower than the upper limit value, the visibility of the engraving of the protective film or the film for forming a protective film through the support sheet can be improved.

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

The L value of the adhesive layer can be appropriately adjusted within the range set in any combination of the above-described preferred lower limit value and upper limit value. For example, the L value of the adhesive layer is preferably 2.5 to 9 μm, more preferably 2.5 to 8.6 μm, and particularly preferably 2.5 to 8.3 μm, such as 2.5 to 7.7 μm, 2.5 to 7.3 μm, 2.5 to 6.9 μm, and 2.5 to Any one of 6.5μm.

The thickness of the adhesive layer (for example, T _a ) is mentioned before it is not damaged and the effects of the present invention are not particularly limited, and it is preferable to satisfy the above-mentioned conditions of the S value and the L value. For example, the thickness of the adhesive layer may also be 1.5-9 μm.

In addition, the "thickness of the adhesive layer" refers to the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers refers to the total thickness of all layers constituting the adhesive layer. From this viewpoint, the minimum and maximum thicknesses of the adhesive layer are specified.

The adhesive layer contains an adhesive. Examples of the adhesive system include acrylic resins, urethane resins, rubber resins, polysiloxane resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. Acrylic resins are preferred.

In this specification, the term "adhesive resin" includes the concepts of both adhesive resins and adhesive resins. For example, not only those resins that have adhesive properties but also resins that exhibit adhesion by using additives such as additives in combination. , Resins that exhibit adhesion by the presence of a trigger such as heat or water.

The adhesive layer is preferably transparent. The adhesive layer can also be colored according to the purpose. For example, when the thin film for forming a protective film is hardenable by an energy ray, it is preferable that the adhesive layer penetrate the energy ray.

The adhesive layer may be formed using an energy ray hardening adhesive, or may be formed using a non-energy ray hardening adhesive. Adhesive layer formed with energy ray hardening adhesive can easily adjust the physical properties before and after hardening.

＜＜Adhesive composition＞＞ The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition is coated on the surface of the adhesive layer where the target is formed, and if necessary, dried, the adhesive layer can be formed at the target site. The more specific method of forming the adhesive layer will be described in detail later together with the method of forming the outer layer. The content ratio between components in the adhesive composition that does not vaporize at ordinary temperature is usually the same as the content ratio between the above components in the adhesive layer.

In this specification, the "normal temperature" refers to a temperature that is not particularly cold or particularly hot, that is, an ordinary temperature, for example, a temperature of 15 to 25°C.

The coating system of the adhesive composition can be implemented by a known method, for example, using an air knife coating machine (Air-knife-coater), a blade coater (Blade-coater), a bar coater (Bar-coater), Gravure-coater, roll-coater, roll-knife-coater, curtain-coater, die coater -Coater), Knife-coater, Screen-coater, Meyer-bar-coater, Kiss-coater, etc. Cloth machine method.

The drying conditions of the adhesive composition are not particularly limited, and when the adhesive composition contains a solvent described later, it is preferable to perform heat drying. The adhesive composition containing a solvent is preferably dried under conditions such as 70 to 130° C. for 10 seconds to 5 minutes.

When the adhesive layer is energy ray curable, the adhesive composition containing the energy ray curable adhesive (ie, the energy ray curable adhesive composition) can be exemplified by: containing non-energy ray curable adhesive Resin (I-1a) (hereinafter referred to as "adhesive resin (I-1a)"), an adhesive composition (I-1) with an energy ray-curable compound; contains a non-energy ray-curable adhesive resin (I-1a) I-1a) Adhesive composition (I-2) of energy ray-curable adhesive resin (I-2a) (hereinafter referred to as "adhesive resin (I-2a)") in which unsaturated groups are introduced into the side chain; contains The adhesive composition (I-3) of the above adhesive resin (I-2a) and the energy ray-curable compound, etc.

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

[Adhesive resin (I-1a)] The adhesive resin (I-1a) is preferably an acrylic resin. Examples of the acrylic resin include acrylic polymers having at least structural units derived from alkyl (meth)acrylate. The structural unit system of the acrylic resin may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio system may be arbitrarily selected.

Examples of the alkyl (meth)acrylate include those having 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched. More (meth)acrylic acid alkyl esters include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-butyl meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate , Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), ( Tridecyl meth)acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetane (meth)acrylate Ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), deca(meth)acrylate Nine alkyl esters, eicosyl (meth) acrylate, etc.

From the viewpoint of enhancing the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from the alkyl (meth)acrylate having 4 or more alkyl carbon atoms. However, from the viewpoint of further enhancing the adhesive force of the adhesive layer, the carbon number of the alkyl group is preferably 4-12, and more preferably 4-8. In addition, the alkyl (meth)acrylate having an alkyl carbon number of 4 or more is preferably an alkyl acrylate.

In addition to the structural units derived from the alkyl (meth)acrylate, the acrylic polymer preferably has structural units derived from the functional group-containing monomer. Examples of the functional group-containing monomer include reaction of the functional group with a cross-linking agent described later to become a cross-linking starting point, and reaction of the functional group with an unsaturated group in an unsaturated group-containing compound described below. An unsaturated group is introduced into the side chain of the acrylic polymer.

Examples of the functional group system in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amine group, and an epoxy group. That is, the functional group-containing single system includes, for example, hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, epoxy group-containing monomers, and the like.

Examples of the above-mentioned hydroxyl-containing single system include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid-3 -Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. ; Non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton) etc.

Examples of the carboxyl-containing monosystem include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, cis Ethylene unsaturated dicarboxylic acids such as butenedioic acid and citraconic acid (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. Carboxyalkyl (meth)acrylate and the like.

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

The functional group-containing single system constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio system may be arbitrarily selected.

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

In addition to the structural units derived from the alkyl (meth)acrylate and the structural units derived from the functional group-containing monomer, the acrylic polymerization system may further have structural units derived from other monomers. The other single system mentioned above is not particularly limited until it can be copolymerized with alkyl (meth)acrylate or the like. Examples of the other single systems include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylic amide.

The other single systems constituting the acrylic polymer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio system may be arbitrarily selected.

The acrylic polymer system can be used as the non-energy ray-curable adhesive resin (I-1a). On the other hand, if the functional group in the acrylic polymer and the unsaturated group having an energy ray polymerizable unsaturated group (energy ray polymerizable group) contain a compound generator, the energy ray-curable adhesive resin can be used (I-2a).

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

In the adhesive composition (I-1), the content of the 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.

[Energy Ray Hardening Compound] The energy ray-curable compound contained in the adhesive composition (I-1) may be, for example, a monomer or an oligomer that has an energy ray polymerizable unsaturated group and can be cured by irradiation with energy ray. Among the energy ray-curable compounds, the single system may be exemplified by trimethylolpropane tri[(meth)acrylate], neopentyl alcohol (meth)acrylate, neopentyl alcohol tetra[(methyl) Acrylate], dipentaerythritol hexa[(meth)acrylate], 1,4-butanediol di[(meth)acrylate], 1,6-hexanediol (meth)acrylate, etc. Poly(meth)acrylate; urethane (meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray-curable compounds, oligomers include oligomers obtained by polymerizing the above-exemplified monomers. The energy ray-curable compound is preferably urethane (meth)acrylate, urethane (meth)acrylate from the viewpoint of having a large molecular weight and not easy to reduce the storage elastic modulus of the adhesive layer. Oligomer.

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

In the 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 the adhesive resin (I-1a) is a structural unit derived from an alkyl (meth)acrylate, and the acrylic polymer having the structural unit derived from a functional group-containing monomer is further used, the adhesive composition The substance (I-1) preferably further contains a crosslinking agent.

The above-mentioned cross-linking agent reacts with the above-mentioned functional group, for example, and causes the adhesive resins (I-1a) to cross-link with each other. Examples of the crosslinking agent system include isocyanate-based crosslinking agents such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates. (Crosslinking agent); epoxy-based crosslinking agent such as ethylene glycol glycidyl ether (crosslinking agent with glycidyl group); hexa[1-(2-methyl)-aziridinyl]triphosphate triphosphate Azine and other aziridine-based cross-linking agents (cross-linking agents with aziridine group); metal chelate-based cross-linking agents such as aluminum chelate (cross-linking agents with metal chelation structure); isocyanurates It is a cross-linking agent (cross-linking agent with isocyanuric acid skeleton), etc. From the viewpoints of enhancing the cohesive force of the adhesive, improving the adhesion of the adhesive layer, and easily available, the crosslinking agent is preferably an isocyanate-based crosslinking agent.

The crosslinking agent system contained in the adhesive composition (I-1) may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio system may be arbitrarily selected.

In the above adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a). 、 0.3~15 parts by mass of Tejia.

[Photopolymerization initiator] The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a hardening reaction even when irradiated with a lower energy energy line such as ultraviolet rays.

等氧硫𠮿

化合物；過氧化合物；二乙醯等二酮化合物；苄基；二苄基；二苯基酮；2,4-二乙基氧硫𠮿

；1,2-二苯甲烷；2-羥-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。 再者，上述光聚合起始劑亦可使用例如：1-氯蒽醌等醌化合物；胺等光增感劑等。Examples of the photopolymerization initiator system include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoin Methyl acid, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy- Acetophenone compounds such as 1,2-diphenylethane-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzene Acetyl phosphine oxide compounds such as methyl diphenyl phosphine oxide; thio ether compounds such as benzyl phenyl sulfide, tetramethylamine thiomethyl monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl benzophenone; azo Azo compounds such as bisisobutyronitrile; titaniumocene compounds such as titanocene; oxygen and sulfur 𠮿

Isotope sulfur 𠮿

Compounds; Peroxy compounds; Diketones such as diethyl acetyl; benzyl; dibenzyl; diphenyl ketone; 2,4-diethyl oxysulfide

; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone and so on. In addition, as the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a light sensitizer such as amine; and the like can also be used.

The photopolymerization initiator system contained in the adhesive composition (I-1) may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio system may be arbitrarily selected.

In the 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 relative to 100 parts by mass of the energy ray-curable compound content. The special grade is 0.05~5 parts by mass.

[Other additives] The adhesive composition (I-1) is within the range not detrimental to the effects of the present invention, and may contain other additives not belonging to any of the above-mentioned components. Examples of the above-mentioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reaction resistance Known additives such as retarders and crosslinking accelerators (catalysts). In addition, the so-called "reaction retarder" is to prevent unintended crosslinking of the adhesive composition (I-1) during storage due to, for example, the catalyst action mixed in the adhesive composition (I-1) reaction. The reaction retarder may be, for example, a chelate complex formed by a chelate on a catalyst, and more specifically, one having two or more carbonyl groups (-C(=O)-) in one molecule.

The other additive system contained in the adhesive composition (I-1) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected.

The content of other additives in the adhesive composition (I-1) is not particularly limited, as long as the type of compounding is appropriately selected.

[Solvent] The adhesive composition (I-1) may contain a solvent. By containing a solvent, the adhesive composition (I-1) improves the coating suitability for the surface to be coated.

The above solvent is preferably an organic solvent. Examples of the above organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; and fats such as cyclohexane and n-hexane. Group hydrocarbons; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol;

The above-mentioned solvent system can be directly used for the adhesive composition (I-1) without removing from the adhesive resin (I-1a) when the user does not remove the adhesive resin (I-1a) during the manufacture of the adhesive resin (I-1a). In the production of the agent composition (I-1), a solvent of the same or different type as the user used in the production of the adhesive resin (I-1a) is separately added.

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

The solvent content in the adhesive composition (I-1) is not particularly limited, as long as it is adjusted appropriately.

<Adhesive composition (I-2)> The adhesive composition (I-2) is as described above and contains an energy ray-curable adhesive resin (I-2a) after introducing an unsaturated group into the side chain of the non-energy ray-curable adhesive resin (I-1a) .

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

The above-mentioned unsaturated group-containing compound is in addition to the above-mentioned energy ray polymerizable unsaturated group, and further has a functional group in the adhesive resin (I-1a) to react with the adhesive resin (I-1a) Bonding compound. Examples of the energy ray polymerizable unsaturated group system include (meth)acryloyl group, vinyl group (also known as "ethenyl group"), allyl group (also known as "2-propenyl group"), etc. Preferred systems (Meth) acrylamide. The group capable of bonding with the functional group in the adhesive resin (I-1a) includes, for example, isocyanate group and epoxypropyl group which can bond with hydroxyl group or amine group, and bond with carboxyl group or epoxy group Bonded hydroxyl and amine groups.

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

The adhesive resin (I-2a) contained in the 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, the combination and ratio system may be arbitrarily selected.

The content of the adhesive resin (I-2a) in the adhesive composition (I-2) is preferably 5 to 99% by mass and more preferably 10 to 95 relative to the total mass of the adhesive composition (I-2) Mass%, 10~90 mass% of Tejia.

[Crosslinking agent] For the adhesive resin (I-2a), for example, the above-mentioned acrylic polymer having a structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1a), the adhesive composition (I-2 ) May further contain a crosslinking agent.

The crosslinking agent in the adhesive composition (I-2) may be the same as the crosslinking agent in the adhesive composition (I-1). The crosslinking agent system contained in the adhesive composition (I-2) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected.

The content of the cross-linking agent in the adhesive composition (I-2) is preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). The super good line is 0.3~15 parts by mass.

[Photopolymerization initiator] The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator is sufficiently cured even when irradiated with low-energy energy rays such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-2) may be the same as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator system contained in the 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, the combination and ratio system may be arbitrarily selected.

The content of the photopolymerization initiator in the adhesive composition (I-2) is preferably 0.01-20 parts by mass and more preferably 0.03-10 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). 、0.05~5 parts by mass of Tejia.

[Other additives] The adhesive composition (I-2) is within the range not detrimental to the effects of the present invention, and may contain other additives not affiliated with any of the above-mentioned components. The other additives in the adhesive composition (I-2) may be the same as the other additives in the adhesive composition (I-1). The other additive system contained in the adhesive composition (I-2) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected.

The content of other additives in the adhesive composition (I-2) is not particularly limited, as long as the type of compounding is appropriately selected.

[Solvent] The adhesive composition (I-2) may contain a solvent for the same purpose as the adhesive composition (I-1). The solvent in the adhesive composition (I-2) may be the same as the solvent in the adhesive composition (I-1). The solvent system contained in the 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, the combination and ratio system may be arbitrarily selected. The solvent content in the adhesive composition (I-2) is not particularly limited, as long as it is adjusted appropriately.

<Adhesive composition (I-3)> The adhesive composition (I-3) is as described above, and contains the adhesive resin (I-2a) and the energy ray-curable compound.

The content of the adhesive resin (I-2a) in the adhesive composition (I-3) is preferably 5 to 99% by mass and more preferably 10 to 95 relative to the total mass of the adhesive composition (I-3) Mass %, 15~90 mass% of the special good department.

[Energy Ray Hardening Compound] The above energy ray-curable compounds contained in the adhesive composition (I-3) include monomers and oligomers which have an energy-ray polymerizable unsaturated group and can be hardened by irradiation with energy rays, and examples include adhesives The energy ray-curable compound contained in the composition (I-1) is the same. The energy ray-curable compound contained in the adhesive composition (I-3) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected.

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

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

The photopolymerization initiator in the adhesive composition (I-3) may be the same as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator system contained in the adhesive composition (I-3) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected.

The content of the photopolymerization initiator in the adhesive composition (I-3) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the above energy ray-curable compound. , More preferably, it is 0.03~10 parts by mass, and especially, it is 0.05~5 parts by mass.

[Other additives] The adhesive composition (I-3) is within the range that does not damage and the effect of the present invention, and may contain other additives that are not affiliated with any of the above components. The other additives mentioned above may be the same as the other additives in the adhesive composition (I-1). The other additive system contained in the adhesive composition (I-3) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected.

The content of other additives in the adhesive composition (I-3) is not particularly limited, as long as the type of compounding is appropriately selected.

[Solvent] The adhesive composition (I-3) may contain a solvent for the same purpose as the adhesive composition (I-1). The solvent system contained in the adhesive composition (I-3) may be only one type, or may be two or more types, and in the case of two or more types, the combination and ratio system may be arbitrarily selected. The solvent content in the adhesive composition (I-3) is not particularly limited, as long as it is adjusted appropriately.

<Adhesive composition other than adhesive composition (I-1) to (I-3)> Up to now, it mainly focuses on the adhesive composition (I-1), the adhesive composition (I-2) and the adhesive composition (I-3), but these described components can still be used here. All adhesive compositions other than the three types of adhesive compositions (also referred to as "adhesive compositions other than adhesive compositions (I-1) to (I-3)" in this specification).

The adhesive composition other than the adhesive compositions (I-1) to (I-3) is an energy ray-curable adhesive composition, and non-energy ray-curable adhesive compositions can also be cited. The non-energy ray-curable adhesive composition system includes, for example, acrylic resin, urethane resin, rubber resin, polysiloxane resin, epoxy resin, polyvinyl ether, polycarbonate, ester The adhesive composition (I-4) of a non-energy ray-curable adhesive resin (I-1a) such as a resin is preferably an acrylic resin.

The adhesive composition other than the adhesive composition (I-1) to (I-3) preferably contains one kind or two or more kinds of crosslinking agents, and the content can be set as the above-mentioned adhesive composition ( I-1) etc. are the same.

＜Adhesive composition (I-4)＞ The adhesive composition (I-4) preferably includes, for example, those containing the above-mentioned adhesive resin (I-1a) and a crosslinking agent.

[Adhesive resin (I-1a)] The adhesive resin (I-1a) in the adhesive composition (I-4) may be the same as the adhesive resin (I-1a) in the adhesive composition (I-1). The adhesive resin (I-1a) system contained in the 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, the combination and ratio system may be arbitrarily selected.

The content of the adhesive resin (I-1a) in the adhesive composition (I-4) is preferably 5 to 99% by mass and more preferably 10 to the total mass of the adhesive composition (I-4). 95% by mass, 15-90% by mass of the Tejia line.

In the adhesive composition (I-4), the ratio of the content of the adhesive resin (I-1a) to the total content of all components other than the solvent (ie, the content of the adhesive resin (I-1a) in the adhesive layer) is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and 50 to 80% by mass.

[Crosslinking agent] When the adhesive resin (I-1a) is a structural unit derived from an alkyl (meth)acrylate, and the acrylic polymer having the structural unit derived from a functional group-containing monomer is further used, the adhesive composition The substance (I-4) preferably further contains a crosslinking agent.

The crosslinking agent in the adhesive composition (I-4) may be the same as the crosslinking agent in the adhesive composition (I-1). The crosslinking agent system contained in the adhesive composition (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected.

The content of the crosslinking agent in the adhesive composition (I-4) is preferably 0.01 to 50 parts by mass, and more preferably 0.3 to 50 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a). The super good system is 1-50 parts by mass, for example, any one of 10-50 parts by mass, 15-50 parts by mass, and 20-50 parts by mass.

[Other additives] The adhesive composition (I-4) is within the range that does not damage and the effect of the present invention, and may contain other additives that are not affiliated with any of the above components. The other additives mentioned above may be the same as those in the adhesive composition (I-1). The other additive system contained in the adhesive composition (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected.

The content of other additives in the adhesive composition (I-4) is not particularly limited, as long as the type of compounding is appropriately selected.

[Solvent] The adhesive composition (I-4) may contain a solvent for the same purpose as the adhesive composition (I-1). The solvent in the adhesive composition (I-4) may be the same as the solvent in the adhesive composition (I-1). The solvent system contained in the adhesive composition (I-4) may be only one kind, or may be two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected. The solvent content in the adhesive composition (I-4) is not particularly limited, as long as it is adjusted appropriately.

In the above-mentioned composite sheet for forming a protective film, the adhesive layer is preferably non-energy ray-curable. The reason is that if the adhesive layer is energy ray-curable, when the film for forming a protective film is cured by irradiation with energy ray, the adhesive layer may not be cured simultaneously. If the adhesive layer and the film for forming a protective film are cured at the same time, the film for forming a protective film (that is, the protective film) and the adhesive layer after hardening will be attached at the interface to the extent that they cannot be peeled off. In this case, it is difficult to peel off the semiconductor wafer (semiconductor wafer with a protective film) provided with a thin film for forming a protective film after hardening (ie, a protective film) on the back surface, resulting in the protective film The semiconductor wafer cannot be picked up normally. In the above-mentioned support sheet, the adhesive layer is made non-energy ray hardenable, so that such a defect can be avoided and the semiconductor wafer with a protective film can be picked up more easily.

Although the effect of the adhesive layer system on non-energy ray hardening is described here, even if the layer directly in contact with the protective film forming film of the support sheet is a layer other than the adhesive layer, as long as the layer is non-energy ray hardening Sex, still achieve the same effect.

＜＜Production method of adhesive composition＞＞ Adhesive compositions (I-1) to (I-3), adhesive compositions (I-4) and other adhesive compositions other than adhesive compositions (I-1) to (I-3) It can be obtained by blending the above-mentioned adhesive agent, components other than the above-mentioned adhesive agent, etc., which constitute the adhesive agent composition, as necessary. The order of addition of each component during blending is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent can be mixed with any of the blended components other than the solvent, and then the blended component can be used after pre-dilution, or it can be used without pre-dilution of any blended component other than the solvent. The solvent is mixed with these blending components. At the time of blending, the method of mixing the components is not particularly limited, and for example, a method of rotating a stirrer or a stirring blade and mixing; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, etc. It is appropriately selected from known methods. The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each blending component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15 to 30°C.

◎Protective film forming film The above-mentioned thin film for forming a protective film forms a protective film by curing or uncuring to maintain the original state. This protective film is for protecting the semiconductor wafer or the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface). The thin film for forming a protective film is soft and can be easily attached to the object to be attached.

The thin film system for forming a protective film may be curable or non-curable. The thin film for forming a curable protective film may be any of thermosetting and energy ray hardening, and may have both the characteristics of thermosetting and energy ray hardening. The thin film for forming a protective film can be formed using a composition for forming a protective film containing its constituent material.

In this specification, the term "non-hardening" refers to the property that it does not harden regardless of any means such as heating or energy beam irradiation. In the present invention, even after the thin film for forming a protective film is cured, the laminated structure of the cured product of the support sheet and the thin film for forming a protective film (in other words, the supporting sheet and the protective film) can be maintained. "Composite sheet for forming protective film".

The thin film system for forming a protective film may be composed of one layer (single layer) regardless of the type, or plural layers of two or more layers. When the thin film for forming a protective film is composed of a plurality of layers, these plurality of layers may be the same or different from each other.

Here, referring to FIG. 4 again, the adhesive layer and the thin film for forming a protective film will be described in further detail. As described above, the first surface 11a of the base material 11 is an uneven surface. However, the adhesive layer 12 suppresses the influence of the uneven surface by the S value of 1.5 μm or more, and reduces the unevenness of the first surface 12 a of the adhesive layer 12. For example, even if there are unbonded areas (unbonded areas) 92 between the adhesive layer 12 and the film 13 for forming a protective film, the number of them is across the protective film in the composite sheet 1A for forming a protective film In the total area of the formation region of the thin film 13 for formation, there are still very few conditions such as 3 or less. The non-bonded region 92 can be easily confirmed by viewing the composite sheet 1A for forming a protective film from the base material 11 side, for example.

In addition, even if the composite sheet 1A for protective film formation has such an unattached region 92, the size (maximum interlayer distance) of the unattached region 92 in the thickness direction of the composite sheet 1A for protective film formation is, for example, 0.5 μm or less. In the composite sheet 1A for forming a protective film, the lamination property between the adhesive layer 12 and the film 13 for forming a protective film is better. The "size of the unattached region 92 (maximum interlayer distance)" here refers to "the maximum value of the interlayer distance between the adhesive layer 12 and the protective film forming film 13 in the thickness direction of the protective film forming composite sheet 1A ".

The size of the unattached area 92 (the maximum value of the interlayer distance) is the same as the maximum value (size) of the interlayer distance of the unattached area 91, preferably 0.5 μm or less, for example, 0.4 μm or less, 0.3 μm Any one of the following, 0.2 μm or less, and 0.1 μm or less.

The size of the unattached area 92 (maximum distance between layers) is different from the target two-layer combination, for example, and the rest can be calculated in the same way as the size of the unattached area 91 (maximum distance between layers). take.

In the composite sheet 1A for forming a protective film, there may be no unbonded area 92 at all. In this specification, when the size of the unattached area is greater than 0.05 μm, it is considered that there is an unattached area, but when there is no unattached area 92 at all, the size of the unattached area 92 (interlayer distance ) Case of 0 μm.

On the other hand, as described above, the unevenness of the first surface 12a of the adhesive layer 12 can be easily reduced. Therefore, although the thickness T _{p of the} thin film 13 for forming a protective film is not constant, but the position according to the thin film 13 for forming a protective film (adhesive layer 12) varies, but the range of variation is extremely small.

Furthermore, as described above, since the unevenness of the first surface 12a of the adhesive layer 12 can be easily reduced, the surface 13b of the protective film forming film 13 on the adhesive layer 12 can be easily smoothed or reduced Roughness. Therefore, the appearance of the thin film 13 for forming a protective film is not easily damaged. Therefore, even if the protective film is formed by the thin film 13 for forming a protective film, the side (second side) of the adhesive layer 12 can be smoothed, or the unevenness can be reduced, so that the appearance of the protective film is not easily damaged. Accordingly, in the composite sheet 1A for forming a protective film, both the thin film 13 for forming a protective film and the protective film can be excellent in design.

The second surface 13b of the thin film 13 for forming a protective film, the maximum height difference between the highest part of the convex part and the deepest part of the concave part is preferably 2 μm or less, for example, any one of 1.5 μm or less and 1 μm or less. The thin film 13 for forming a protective film and the protective film are particularly excellent in design.

The above-mentioned maximum height difference of the second surface 13b of the thin film 13 for protective film formation is, for example, the cross-section of the test piece of the composite film for protective film formation or the composite film for protective film formation is formed by itself using the method described above, and then used Scanning electron microscope (SEM) can be obtained by observing this cross section.

Although the protective sheet forming composite sheet 1A is taken as an example here, the adhesive layer and the protective film forming film will be described, but regarding the protection of other embodiments such as the protective sheet forming composite sheet 1B and the protective film forming composite sheet 1C In the case of the composite sheet for film formation, the same is the same as the adhesive layer and the film for forming the protective film.

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 particularly preferably 5 to 50 μm. When the thickness of the thin film for forming a protective film exceeds the above lower limit value, a protective film with higher protective capacity can be formed. When the thickness of the thin film for forming a protective film is equal to or less than the above upper limit, the thickness is suppressed from being too thick.

When the thickness of the thin film for protective film formation varies depending on the position of the thin film for protective film formation, the minimum thickness of the thin film for protective film formation may be above the lower limit, and the thickness of the thin film for protective film formation The maximum value may be below the above upper limit.

In addition, the "thickness of the thin film for protective film formation" refers to the thickness of the entire thin film for protective film formation, for example, the thickness of the thin film for protective film formation consisting of a plurality of layers, refers to the thickness of all layers constituting the thin film for protective film formation Total thickness.

The thickness of the thin film for protective film formation can be measured by observing the side surface or cross section of the thin film for protective film formation using, for example, a scanning electron microscope (SEM). The cross-section of the thin film for protective film formation can be formed in the same manner as in the case of the cross-section of the test piece of the support sheet and the composite sheet for protective film formation, for example.

For example, using the method described above, the test piece is cut from a plurality of places (for example, 5 places) of the composite film for forming a protective film, and the minimum and maximum thickness of the film for forming the protective film is obtained for this test piece, and then from When these minimum and maximum average values are obtained from these numerical values, the minimum average value can be equal to or greater than the lower limit of the thickness of the protective film forming film, and the maximum average value can be in the protective film forming film Below the upper limit of the thickness.

The thin film for forming a protective film can be formed using a composition for forming a protective film containing its constituent material. For example, the protective film-forming composition is applied to the target-forming surface of the protective film-forming thin film, and if necessary, dried, the protective film-forming thin film can be formed at the target site. The content ratio between the components that do not vaporize at normal temperature in the composition for forming a protective film is usually the same as the content ratio between the above-mentioned components of the film for forming a protective film.

The coating system of the protective forming composition can be implemented by a known method, for example, using an air knife coater, a knife coater, a bar coater, a gravure coater, a roll coater, a roll knife coater , Curtain coater, die coater, knife coater, screen coater, Mailer bar coater, stapling coater and other coating methods.

The drying conditions of the composition for forming a protective film are not particularly limited, and when the composition for forming a protective film contains a solvent described later, it is preferably dried by heating. In addition, the composition for forming a protective film containing a solvent is preferably dried under conditions of, for example, 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 formed thin film for forming a protective film will not be thermally cured.

Hereinafter, the thin film for forming a protective film and the composition for forming a protective film will be described in detail according to types.

○Thin film for thermosetting protective film formation Preferred films for forming a thermosetting protective film include those containing a polymer component (A) and a thermosetting component (B). The polymer component (A) can be regarded as a component formed by a polymerization reaction of a polymerizable compound. The thermosetting component (B) is a component that can undergo a curing (polymerization) reaction using heat as a trigger for the reaction. In addition, the polymerization reaction of the present invention also includes polycondensation reaction.

After attaching the film for forming a thermosetting protective film to the back surface of the semiconductor wafer, the curing conditions at the time of thermosetting are not particularly limited as long as the cured product has a curing degree that fully exerts its function, and can be combined The type of the thin film for forming a thermosetting protective film can be appropriately selected. 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. In addition, the heating time during 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 thermosetting protective film (III-1)> A preferred composition for forming a thermosetting protective film includes, for example, a composition (III-1) for forming a thermosetting protective film containing a polymer component (A) and a thermosetting component (B) (in this specification) Also referred to as "Composition (III-1)") etc.

[Polymer component (A)] The polymer component (A) is a component for imparting film-forming properties, flexibility, and the like to the thin 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 kind, or two or more kinds, and if two or more kinds, the combination of The ratio is optional.

Examples of the polymer component (A) include acrylic resin, polyester, urethane resin, urethane acrylate resin, polysiloxane resin, rubber resin, phenoxy resin, thermosetting polymer Acetylene and the like are preferably acrylic resins.

The acrylic resin in the polymer component (A) may be a known acrylic polymer. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is at least the above lower limit, the shape stability of the film for forming a thermosetting protective film (time stability during storage) is improved. In addition, when the weight average molecular weight of the acrylic resin is below the upper limit, the film for forming a thermosetting protective film can easily follow the uneven surface of the adherend, thereby further suppressing the formation of the adherend and the thermosetting protective film Porosity occurs between the films.

In this specification, the "weight average molecular weight" refers to the conversion value of polystyrene measured by the gel permeation chromatography (GPC) method unless otherwise stated.

The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70°C, more preferably -30 to 50°C. When the Tg of the acrylic resin is equal to or higher than the above lower limit, for example, the adhesive force between the cured product of the protective film forming film (ie, the protective film) and the support sheet is suppressed, so that the peelability of the support sheet is appropriately improved. In addition, when the Tg of the acrylic resin is below the above upper limit, the adhesion between the thermosetting protective film forming film and the adherend of the protective film is improved. In addition, it is not limited to the acrylic tree. The resin Tg system in this specification uses, for example, a differential scanning calorimeter (DSC), the heating rate or the cooling rate is set to 10°C/min, and the temperature of the measurement target is -70°C to 150°C. The change between ℃ can be obtained by confirming the inflection point.

Examples of acrylic resins include: polymers of one or more (meth)acrylates; from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol Among acrylamide and the like, copolymers of two or more monomers are selected.

The (meth)acrylate constituting the acrylic resin may be, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (A Group) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid N-nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) ), tridecyl (meth)acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth)acrylic acid Cetyl ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group of the base ester is a chain structure alkyl (meth)acrylate having 1 to 18 carbon atoms; Cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; Aryl (meth)acrylate such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylate such as (cyclopentenyl) (meth)acrylate; (Meth)acrylic acid cyclopentenyloxyalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate; (Meth)acrylic acid imide; (Meth)acrylic acid esters such as glycidyl acrylate (meth)acrylate; Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid Hydroxy-containing (meth)acrylates such as -2-hydroxybutyl ester, (meth)acrylic acid 3-hydroxybutyl ester, (meth)acrylic acid 4-hydroxybutyl ester; (Meth)acrylic acid-N-methylaminoethyl ester, etc. (meth)acrylic acid ester containing substituted amine groups, etc. Here, the "substituted amine group" refers to a group in which one or two hydrogen atoms of the amine group are substituted with groups other than hydrogen atoms.

Acrylic resins can be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-hydroxymethylacrylamide, etc. One or more than two monomers are selected and copolymerized.

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

The acrylic resin may have functional groups capable of bonding with other compounds, such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups. The above-mentioned functional group system of the acrylic resin may be bonded to other compounds via a cross-linking agent (F) described later, or may be directly bonded to other compounds without the cross-linking agent (F). By bonding the acrylic resin to other compounds by using the above functional groups, there is a tendency to increase the reliability of the encapsulation obtained by using the composite sheet for forming a protective film.

In the present invention, in the case where the acrylic resin is not used for the polymer component (A), thermoplastic resins other than acrylic resins (hereinafter also simply referred to as "thermoplastic resins") may be used alone, or acrylic resins may be used in combination. By using the above-mentioned thermoplastic resin, the peelability of the protective film from the support sheet is improved, and the film for forming a thermosetting protective film easily follows the uneven surface of the adherend, etc., and the adherend and thermosetting property may be more suppressed Porosity or the like occurs between the thin films for protective film formation.

The weight average molecular weight of the thermoplastic resin is preferably 1,000 to 100,000, and more preferably 3,000 to 80,000.

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 above-mentioned thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio system Can be chosen arbitrarily.

In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components except the solvent (that is, the content of the polymer component (A) of the film for forming a thermosetting protective film), regardless of the polymer The types of component (A) are 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, etc. Any one.

The polymer component (A) may also belong to the thermosetting component (B). In the present invention, when the composition (III-1) contains such a component that belongs to both the polymer component (A) and the thermosetting component (B), it is deemed that the composition (III-1) contains polymerization Body composition (A) and thermosetting composition (B).

[Thermosetting component (B)] The thermosetting component (B) is a component for curing the thin 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, or two or more types, and if two or more types are used, the combination The ratio can be selected arbitrarily.

Examples of the thermosetting component (B) include epoxy thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, polysiloxane resin, etc., preferably epoxy thermosetting resin Resin.

(Epoxy thermosetting resin) The epoxy-based thermosetting resin system is composed of an epoxy resin (B1) and a thermosetting agent (B2). The composition (III-1) and the thermosetting epoxy resin contained in the film for forming a thermosetting protective film may be only one type, or two or more types, and if two or more types are used, the combination The ratio can be chosen arbitrarily.

‧Epoxy resin (B1) Examples of the epoxy resin (B1) include publicly known substances, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-cresol novolac epoxy resins, dicyclopentane Diene-type epoxy resins, biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, phenylene skeleton-type epoxy resins and other epoxy functional compounds with more than two functional groups.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The compatibility of epoxy resins with unsaturated hydrocarbon groups with acrylic resins is higher than that with epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the semiconductor wafer with a protective film obtained by using the composite film for forming a protective film can be improved.

Examples of the epoxy resin system having an unsaturated hydrocarbon group include a compound formed by converting a partial epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by adding (meth)acrylic acid or a derivative thereof to an epoxy group. In addition, examples of the epoxy resin group having an unsaturated hydrocarbon group include a compound having an unsaturated hydrocarbon group directly bonded to an aromatic ring constituting the epoxy resin. The unsaturated hydrocarbon group has a polymerizable unsaturated group, and specific examples include, for example, vinyl (ethenyl group), 2-propenyl (allyl), (meth)acryloyl, (meth)acryloyl The amine group and the like are preferably acrylamide.

The number average molecular weight of the epoxy resin (B1) is not particularly limited. From the viewpoint of the curability of the thermosetting protective film forming film and the strength and heat resistance of the protective film after curing, it is preferably 300 to 30,000. The best series is 300~10000, and the best series is 300~3000.

In this specification, the "number-average molecular weight" refers to the conversion value of polystyrene measured by the gel permeation chromatography (GPC) method unless otherwise stated.

The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g/eq, more preferably 150 to 950 g/eq. In this specification, the "epoxy equivalent" refers to the gram number (g/eq) of an epoxy compound containing 1 gram equivalent of epoxy groups, and can be measured according to the method of JIS K 7236:2001.

One type of epoxy resin (B1) may be used alone, or two or more types may be used in combination. If two or more types are used in combination, the combination and ratio system may be arbitrarily selected.

‧Heat hardener (B2) The thermosetting agent (B2) has the function of a curing agent for the epoxy resin (B1). The thermosetting agent (B2) includes compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group system include phenolic hydroxyl groups, alcoholic hydroxyl groups, amine groups, carboxyl groups, and acidified groups with acid groups, and preferably phenolic hydroxyl groups, amine groups, or acidified groups with acid groups. It is more preferably a phenolic hydroxyl group or an amine group.

Among the thermosetting agents (B2), examples of the phenolic curing agent system having a phenolic hydroxyl group include polyfunctional phenol resin, biphenyl, novolac type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type Phenol resin etc. Among the thermosetting agents (B2), examples of the amine-based curing agent having an amine group include dicyandiamide and the like.

The thermal hardener (B2) may have an unsaturated hydrocarbon group. The thermosetting agent (B2) having an unsaturated hydrocarbon group includes, for example, a compound in which a part of hydroxyl groups of a phenol resin is replaced by a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin Compounds formed, etc. The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.

When the phenolic hardener is used as the thermosetting agent (B2), from the viewpoint of improving the peelability of the protective film from the support sheet, the thermosetting agent (B2) is preferably one having a higher softening point or glass transition temperature.

In the thermosetting agent (B2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolac type phenol resin, dicyclopentadiene type phenol resin, and aralkyl type phenol resin is preferably 300 to 30,000 , 400~10000 better, 500~3000 especially good. In the thermosetting agent (B2), the molecular weights of non-resin components such as biphenyl and dicyandiamide are not particularly limited, but are preferably 60 to 500, for example.

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

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) relative to the content of the epoxy resin (B1) is 100 parts by mass, preferably 0.1 to 500 parts by mass, more It is preferably 1 to 200 parts by mass, 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. When the content of the thermosetting agent (B2) reaches the above lower limit or more, the thermosetting protective film forming film is more easily cured. In addition, when the content of the thermosetting agent (B2) is below the upper limit, the moisture absorption rate of the film for forming a thermosetting protective film is reduced, and the reliability of packaging obtained by using the composite sheet for forming a protective film is further improved.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to the polymer The content of component (A) is 100 parts by mass, preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and particularly preferably 40 to 150 parts by mass, such as 45 to 100 parts by mass, and 50 to 80 parts by mass Any of the shares. When the content of the thermosetting component (B) is within this range, for example, the adhesive force between the cured product of the protective film forming 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 thin film for forming a thermosetting protective film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing speed of the composition (III-1). Preferred hardening accelerators (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles with one or more hydrogen atoms replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (one or more hydrogen atoms are replaced by organic groups) Substituted phosphines); tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate and other tetraphenylborate.

The composition (III-1) and the curing accelerator (C) contained in the film for forming a thermosetting protective film may be only one kind, or two or more kinds, and if two or more kinds, the combination of The ratio is optional.

When the hardening accelerator (C) is used, in the composition (III-1) and the film for forming a thermosetting protective film, the content of the hardening accelerator (C) is 100 parts by mass relative to the content of the thermosetting component (B) It is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass. When the above content of the hardening accelerator (C) reaches the above lower limit value, the effect caused by the use of the hardening accelerator (C) can be made more obvious. In addition, when the content of the hardening accelerator (C) is below the upper limit, for example, the suppression of segregation of the high-polarity hardening accelerator (C) in the film for forming a thermosetting protective film under high temperature and high humidity conditions The effect of moving toward the next interface with the adherend further enhances the reliability of the semiconductor wafer with a protective film obtained by using the composite film for forming a protective film.

[Filling material (D)] The composition (III-1) and the thin film for forming a thermosetting protective film may contain a filler (D). The thin film for forming a thermosetting protective film contains the filler (D), so that the water absorption rate and the change rate of the adhesive force can be more easily adjusted within the target range. In addition, by containing the filler (D), the film for thermosetting protective film formation and the protective film can more easily adjust the coefficient of thermal expansion. By using this coefficient of thermal expansion for the formation of the film for thermosetting protective film or the formation of the protective film The optimization of the target object further enhances the reliability of the semiconductor wafer with a protective film obtained by using the composite film for forming a protective film. In addition, the thin film for forming a thermosetting protective film can also reduce the moisture absorption rate of the protective film and improve heat dissipation by containing the filler (D).

The filler (D) may be either an organic filler or an inorganic filler, and is preferably an inorganic filler. Preferred inorganic filler materials include, for example, silica, alumina, talc, calcium carbonate, titanium white, iron oxide red, silicon carbide, boron nitride and other powders; spheres obtained by spheroidizing these inorganic filler materials; Surface modification of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. 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 only one kind, or two or more kinds, and if two or more kinds, the combination and ratio The department can be chosen arbitrarily.

When the filler (D) is used, in the composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, the filler of the film for forming a thermosetting protective film ( D) Content), preferably 5 to 80 mass%, more preferably 10 to 70 mass%, for example, any one of 20 to 65 mass%, 30 to 65 mass%, 40 to 65 mass%, etc. When the content of the filler (D) is within this range, the above-mentioned thermal expansion coefficient can be adjusted more easily, and the strength of the protective film forming film and the protective film can be further improved.

[Coupling agent (E)] The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). The coupling agent (E) can improve the adhesion and adhesion of the thermosetting protective film-forming film to the adherend by using a functional group capable of reacting with an inorganic compound or an organic compound. Furthermore, by using the coupling agent (E), the cured product (protective film) of the thermosetting protective film forming film improves the water resistance without impairing the heat resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group possessed by the polymer component (A), thermosetting component (B), etc., and more preferably a silane coupling agent. Examples of the preferred silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Propyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyl Methyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfonamide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, ethylene triethoxysilane, imidazole silane, etc.

The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or two or more kinds, and if two or more kinds, the combination and ratio The department can be chosen arbitrarily.

When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the film for forming a thermosetting protective film is relative to the polymer component (A) and the thermosetting component (B ) The total content is 100 parts by mass, preferably 0.03-20 parts by mass, more preferably 0.05-10 parts by mass, and particularly preferably 0.1-5 parts by mass. When the content of the coupling agent (E) exceeds the above lower limit, the dispersibility of the filler (D) to the resin and the adhesion between the thermosetting protective film forming film and the adherend can be improved. Make the effect caused by the use of coupling agent (E) more obvious. In addition, when the content of the coupling agent (E) is below the upper limit, the occurrence of outgassing is further suppressed.

[Crosslinking agent (F)] When the polymer component (A) uses the above-mentioned acrylic resins and the like, it has functional groups such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can bond with other compounds. The film for forming the substance (III-1) and the thermosetting protective film may contain a crosslinking agent (F). The cross-linking agent (F) is a component for cross-linking the above functional groups in the polymer component (A) with other compounds, and by cross-linking in this way, the film for forming a thermosetting protective film can be adjusted The initial adhesion and cohesion.

Examples of the crosslinking agent (F) system include organic polyisocyanate compounds, organic polyimide compounds, metal chelate crosslinkers (crosslinkers with metal chelate structure), and aziridine crosslinkers (with Aziridine-based cross-linking agent), etc.

Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter these compounds are collectively referred to as "aromatic polyisocyanate compounds, etc."); and the aforementioned aromatic polyisocyanate compounds Compounds such as trimers, isocyanurates, and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyisocyanate compounds with polyol compounds, etc. The above-mentioned "adduct" means the above-mentioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, together with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Reaction products containing low molecular active hydrogen compounds. Examples of the above-mentioned adducts include the adducts of trimethylolpropane dixylylene diisocyanate as described below. In addition, the "terminal isocyanate urethane prepolymer" is as explained above.

The above-mentioned organic polyisocyanate compounds can be more systematically exemplified by: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-diisocyanatoxylylene; 1, 4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophor Ketone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; in all or part of the hydroxyl groups of polyhydric alcohols such as trimethylolpropane, add two Toluene isocyanate, hexamethylene diisocyanate and any one or more than two compounds of diphenyl isocyanate; diamine diisocyanate, etc.

Examples of the organic polyimine compound system include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridine Propionate, tetramethylolmethane-tri-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylidene melamine Wait.

When the organic polyisocyanate compound is used as the crosslinking agent (F), the polymer component (A) preferably uses a hydroxyl group-containing polymer. When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the thermosetting property can be easily protected by the reaction of the crosslinking agent (F) and the polymer component (A) A cross-linked structure is introduced into the film for film formation.

The composition (III-1) and the cross-linking agent (F) contained in the film for forming a thermosetting protective film may be only one kind, or two or more kinds, and if two or more kinds, the combination of The ratio is optional.

When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the composition (III-1) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the polymer component (A). More preferably, it is 0.1 to 10 parts by mass, and especially good is 0.5 to 5 parts by mass. When the above content of the crosslinking agent (F) reaches the above lower limit value, the effect caused by the use of the crosslinking agent (F) can be made more obvious. In addition, when the content of the cross-linking agent (F) is equal to or less than the upper limit value, excessive use of the cross-linking agent (F) can be suppressed.

[Energy Ray Curable Resin (G)] The composition (III-1) may contain an energy ray-curable resin (G). When the film for forming a thermosetting protective film contains an energy ray-curable resin (G), the characteristics can be changed by energy ray irradiation.

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

Examples of the acrylate compound system include trimethylolpropane tri[(meth)acrylate], tetramethylolmethane tetra[(meth)acrylate], and neopentyl tetraol[(methyl) Acrylate], neopentaerythritol tetra[(meth)acrylate], dipentaerythritol monohydroxypenta[(meth)acrylate], dipentaerythritol hexa[(meth)acrylate], 1,4-butanediol di[(meth)acrylate], 1,6-hexanediol di[(meth)acrylate] and other (meth)acrylates containing chain aliphatic skeleton; di( (Meth)acrylates containing cyclic aliphatic skeleton such as dicyclopentyl methacrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di[(meth)acrylate]; oligomerization Ester (meth)acrylate; urethane (meth)acrylate oligomer; epoxy modified (meth)acrylate; polyether (meth)acrylate other than the above polyalkylene glycol (meth)acrylate Base) acrylate; itaconic acid oligomer, etc.

The weight average molecular weight of the energy ray-curable compound is preferably 100 to 30,000, and more preferably 300 to 10,000.

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

The energy ray-curable resin (G) system 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, the combination and ratio system may be arbitrarily selected.

When using the energy ray-curable resin (G), the content of the energy ray-curable resin (G) is preferably 1 to 95% by mass relative to the total content of all components except the solvent in the composition (III-1), and more preferably 5~90% by mass, 10~85% by mass of the Tejia series.

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

等氧硫𠮿

化合物；過氧化合物；二乙醯等二酮化合物；苄基；二苄基；二苯基酮；2,4-二乙基氧硫𠮿

；1,2-二苯甲烷；2-羥-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。 再者，上述光聚合起始劑尚可舉例如：1-氯蒽醌等醌化合物；胺等光增感劑等。Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether , Benzoin benzoin acid, benzoin benzoin methyl ester, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1- Acetophenone compounds such as ketones, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide , 2,4,6-Trimethylbenzyl diphenylphosphine oxide and other sulfonated phosphine oxide compounds; benzyl phenyl sulfide, tetramethylamine thiosulfide monosulfide and other sulfide compounds; 1-hydroxycyclohexyl Α-keto alcohol compounds such as benzophenone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; oxysulfur 𠮿

Isotope sulfur 𠮿

Compounds; Peroxy compounds; Diketones such as diethyl acetyl; benzyl; dibenzyl; diphenyl ketone; 2,4-diethyl oxysulfide

; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone and so on. In addition, the photopolymerization initiator may include, for example, quinone compounds such as 1-chloroanthraquinone; light sensitizers such as amine.

The photopolymerization initiator (H) 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, the combination and ratio system may be arbitrarily selected.

When the photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III-1) is preferably 100 parts by mass relative to the energy ray curable resin (G) content. 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly good 2 to 5 parts by mass.

[Colorant (I)] The composition (III-1) and the film for forming a thermosetting protective film may contain a colorant (I). Examples of the colorant (I) series include known substances such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigments and organic dyes include ammonium pigments, cyanine pigments, merocyanine pigments, croconium pigments, and squaryl cyanine. (Squarylium) pigment, azulenium pigment, polymethine pigment, naphthoquinone pigment, pyrylium pigment, phthalocyanine pigment, naphthalene Naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene ( Perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo pigments, metal complex pigments (metal salt dyes), dithiol metal complex pigments, indole phenol pigments, triallyl methane ( triallyl methane pigment, anthraquinone pigment, bisoxazine pigment, naphthol pigment, azomethine pigment, benzimidazolone pigment, picanthrone (Pyranthrone) pigments and Shirene (threne) pigments.

Examples of the inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, and ITO ( Indium tin oxide) type pigment, ATO (antimony tin oxide) type pigment, etc.

The coloring agent (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or two or more kinds, and if two or more kinds, the combination and ratio The department can be chosen arbitrarily.

When the coloring agent (I) is used, the content of the coloring agent (I) in the film for forming a thermosetting protective film may be adjusted appropriately according to the purpose. For example, by adjusting the content of the coloring agent (I) of the film for forming a thermosetting protective film and adjusting the light permeability of the protective film, the visibility of the marking when laser marking the protective film can be adjusted. Moreover, by adjusting the content of the coloring agent (I) of the thin film for forming a thermosetting protective film, the design of the protective film can also be improved, and the grinding marks on the back surface of the semiconductor wafer are not easily seen. Considering this point, in the composition (III-1), the ratio of the content of the coloring agent (I) to the total content of all components other than the solvent (that is, the content of the coloring agent (I) of the film for forming a thermosetting protective film) It is preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and particularly preferably 0.1 to 5% by mass. When the above content of the colorant (I) reaches the above lower limit value, the effect caused by the use of the colorant (I) can be made more obvious. In addition, when the content of the coloring agent (I) is equal to or less than the upper limit value, the excessive decrease in light permeability of the thin film for forming a thermosetting protective film is suppressed.

[General Additive (J)] The composition (III-1) and the thin film for forming a thermosetting protective film may contain a general-purpose additive (J) as long as it does not damage the effect of the present invention. The general-purpose additive (J) system may be a publicly known product, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples include plasticizers, antistatic agents, antioxidants, gettering agents, and the like.

The general additive (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or may be two or more kinds, and if two or more kinds, the combination and ratio The department can be chosen arbitrarily. The content of the general-purpose additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.

[Solvent] It is preferable that the composition (III-1) further contains a solvent. The disposability of the solvent-containing composition (III-1) was good. The solvent is not particularly limited, and preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropane-1-ol), 1- Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds) )Wait. The solvent system 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, the combination and ratio system may be arbitrarily selected.

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

<<Method for manufacturing composition for forming thermosetting protective film>> The composition for forming a thermosetting protective film such as the composition (III-1) can be obtained by blending the components constituting the same. The order of addition of each component during blending is not particularly limited, and two or more components may be added simultaneously. When using a solvent, the solvent can be mixed with any of the blended components other than the solvent, and then the blended component can be used after pre-dilution. It can also be used without any blended components other than the solvent. Next, the solvent is mixed with these blending components for use. At the time of blending, the method of mixing the components is not particularly limited, and for example, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves It is appropriately selected from known methods. The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each blending component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15 to 30°C.

○ Thin film for forming energy ray curable protective film The film for forming an energy ray-curable protective film includes those containing an energy ray-curable component (a), and preferably contains an energy ray-curable component (a) and a filler. In the thin film for forming an energy ray-curable protective film, the energy ray-curable component (a) is preferably uncured, preferably it has adhesiveness, and more preferably it is uncured and has adhesiveness. Here, the so-called "energy ray" and "energy ray hardenability" are the same as described above.

After the film for forming an energy ray-curable protective film is attached to the back surface of the semiconductor wafer, the curing conditions during curing are not particularly limited as long as the cured product has a degree of curing to the extent that it can fully function. The type of the thin film for forming an energy ray-curable protective film may be selected as appropriate. For example, when the thin film for forming an energy ray-curable protective film is cured, the illuminance of the energy ray is preferably 120 to 280 mW/cm ² . In addition, in the above curing, the luminous flux of the energy ray is preferably 100 to 1000 mJ/cm ² .

<Composition for forming an energy beam curable protective film (IV-1)> A preferred composition for forming an energy ray-curable protective film includes, for example, the composition for forming an energy ray-curable protective film (IV-1) containing the above-mentioned energy ray-curable component (a) (also abbreviated as “abbreviated” in this specification). "Composition (IV-1)") etc.

[Energy ray hardening component (a)] The energy ray-curable component (a) is a component that can be cured by irradiation with energy ray, and also belongs to the film-forming property, flexibility, etc. that is provided to the film for forming an energy ray-curable protective film, and hardened to form a hard protective film Used ingredients. Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000; and a compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000. The polymer (a1) may be cross-linked with a cross-linking agent at least in part, or may not be cross-linked.

(A polymer with an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000 (a1)) Examples of the polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000 include acrylic polymers (a11) having a functional group capable of reacting with groups possessed by other compounds, and having The acrylic resin (a1-1) produced by reacting the functional group generating reaction group and the energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond.

The above functional groups that can react with groups possessed by other compounds include, for example, hydroxyl groups, carboxyl groups, amine groups, and substituted amine groups (one or two hydrogen atoms of an amine group are replaced by groups other than hydrogen atoms) Radical), epoxy, etc. However, from the viewpoint of preventing corrosion of circuits such as semiconductor wafers and semiconductor wafers, the functional group is preferably a group other than a carboxyl group. Among these, the functional group is preferably a hydroxyl group.

‧Acrylic polymer with functional groups (a11) Examples of the acrylic polymer (a11) having the above-mentioned functional group include those formed by copolymerizing an acrylic monomer having the above-mentioned functional group with an acrylic monomer not having the above-mentioned functional group. In addition, it is also possible to copolymerize monomers other than acrylic monomers (non-acrylic monomers). In addition, the said acrylic polymer (a11) system may be a random copolymer or a block copolymer, and a well-known method can also be used for a polymerization method.

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

Examples of the above-mentioned hydroxyl-containing single system include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid-3 -Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. ; Non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols without a (meth)acryloyl skeleton); etc.

Examples of the carboxyl-containing monosystem include: (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids with an ethylenically unsaturated bond); fumaric acid, itaconic acid, cis Ethylene unsaturated dicarboxylic acids such as butenedioic acid and citraconic acid (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the above ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. Carboxyalkyl (meth)acrylate and so on.

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

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

Examples of the acrylic-based single system that does not have the above functional groups include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-butyl meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate , Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as "lauryl (meth)acrylate" "), tridecyl (meth)acrylate, myristyl (meth)acrylate (also known as "myristyl (meth)acrylate"), pentadecyl (meth)acrylate, Cetyl (meth)acrylate (also known as "palmityl (meth)acrylate"), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as "( "Stearyl meth)acrylate"), etc., an alkyl (meth)acrylate alkyl group having a chain structure of 1 to 18 carbon atoms which constitutes an alkyl ester.

In addition, the acrylic monomer which does not have the above-mentioned functional group includes, for example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate (Meth)acrylates containing alkoxyalkyl groups such as esters and ethoxyethyl (meth)acrylates; aromatic groups containing (meth)acrylic acid aryls such as phenyl (meth)acrylates ( Methacrylates; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid-N,N-dimethylaminoethyl, (meth)acrylic acid-N,N-di (Meth) acrylates with non-crosslinkable tertiary amine groups, such as methylaminopropyl esters.

The acrylic monomer that constitutes the acrylic polymer (a11) and does not have the functional group may be only one type, or two or more types, and in the case of two or more types, the combination and ratio system may be arbitrarily selected .

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

In the acrylic polymer (a11), the proportion (content) of the constituent units derived from the acrylic monomer having the functional group with respect to the total constituent units constituting it is preferably 0.1 to 50% by mass , 1~40% by mass of better series, 3~30% by mass of special series. With the above ratio in this range, in the acrylic resin (a1-1) obtained by copolymerizing the acrylic polymer (a11) and the energy ray-curable compound (a12), the energy ray-curable group has The content can easily adjust the hardening degree of the protective film to a better range.

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

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

‧Energy ray hardening compound (a12) In the above energy ray-curable compound (a12), a group capable of reacting with the functional group contained in the acrylic polymer (a11), preferably having a group selected from the group consisting of isocyanate group, epoxy group and carboxyl group One kind or two or more kinds, more preferably, the above-mentioned group has an isocyanate group. The energy ray-curable compound (a12) is, for example, when the group has an isocyanate group, and the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having the functional group as a hydroxyl group.

The energy ray-curable group in one molecule of the energy ray-curable compound (a12) preferably has 1 to 5, and more preferably 1 to 3.

Examples of the energy ray-curable compound (a12) include isocyanato-2-methacryloyloxyethyl, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacryloyl isocyanate. , Allyl isocyanate, 1,1-(bisacryloyloxymethyl) ethyl isocyanate; Acryloyl monoisocyanate compound obtained by reacting diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate; The acrylic monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate is obtained. Among these, the energy ray-curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio system may be arbitrarily selected .

In the acrylic resin (a1-1), the content of the energy ray-curable group derived from the energy ray-curable compound (a12) is relative to that of the functional group derived from the acrylic polymer (a11) The content ratio is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly good 50 to 100 mol%. When the ratio of the above content is within this range, the protective force of the hardened protective film becomes greater. In addition, when the above energy ray-curable compound (a12) is a monofunctional group (the above group has only one in one molecule) compound, the upper limit of the ratio of the above content becomes 100 mol%, but when the above energy ray When the curable compound (a12) is a multifunctional group (the above group has two or more in one molecule), the upper limit of the ratio of the above content will exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.

When at least a part of the polymer (a1) is cross-linked by a cross-linking agent, the polymer (a1) may not belong to any of the above-mentioned monomers described for the formation of the acrylic polymer (a11) It may be polymerized by a monomer having a group that will react with a crosslinking agent, and the group that will react with the above crosslinking agent is crosslinked, or it may be the above energy ray-curable compound (a12) Those derived will undergo crosslinking with groups that react with the above functional groups.

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

(Compound (a2) with an energy ray-curable group and a molecular weight of 100 to 80,000) In the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000, the energy ray-curable group includes a group containing an energy ray-curable double bond, and preferably includes a (meth)acryloyl group and ethylene Base etc.

The compound (a2) is not particularly limited as long as the above conditions are satisfied, and may be, for example, a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, or an energy ray-curable group Of phenol resin etc.

Among the above-mentioned compounds (a2), the low-molecular-weight compound having an energy ray-curable group may include a polyfunctional monomer or oligomer, and the like is preferably an acrylate compound having a (meth)acryloyl group. Examples of the acrylate compound system include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di[(meth)acrylate], propoxylated ethyl Oxidized bisphenol A di[(meth)acrylate], 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di [(Meth)acrylate], 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(methyl) Acryloyloxyethoxy)phenyl] stilbene, 2,2-bis[4-((meth)acryloxypolypropyloxy)phenyl]propane, tricyclodecane dimethanol di[(methyl) Acrylate], 1,10-decanediol di[(meth)acrylate], 1,6-hexanediol di[(meth)acrylate], 1,9-nonanediol di[(methyl ) Acrylate], dipropylene glycol di[(meth)acrylate], tripropylene glycol di[(meth)acrylate], polypropylene glycol di[(meth)acrylate], polybutylene glycol di[(meth) Base) 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 di[(meth)acrylate], ethoxylated polypropylene glycol di[(meth)acrylate ], 2-hydroxy-1,3-di (meth) propyleneoxy propane and other bifunctional (meth) acrylate; Isocyanurate ginseng [2-(meth)acryloxyethyl], ε-caprolactone modified Isocyanurate ginseng [2-(meth)acryloxyethyl], ethoxy Glycerin tris[(meth)acrylate], neopentaerythritol tri[(meth)acrylate], trimethylolpropane tri[(meth)acrylate], di(trimethylolpropane) tetra [(Meth)acrylate], ethoxylated neopentaerythritol tetra[(meth)acrylate], neopentaerythritol tetra[(meth)acrylate], dipentaerythritol poly(methyl ) Multifunctional (meth)acrylates such as acrylate, dipentaerythritol hexa(meth)acrylate; Multifunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers.

Among the above compound (a2), the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group can be, for example, those described in paragraph 0043 of Japanese Patent No. 2013-194102, etc. . Such a resin also belongs to a resin constituting a thermosetting component described later, and is regarded as the above-mentioned compound (a2) in the present invention.

The weight average molecular weight of the compound (a2) is preferably 100 to 30,000, and more preferably 300 to 10,000.

The above-mentioned compound (a2) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film may be only one kind, or two or more kinds, and if two or more kinds, the combination of The ratio is optional.

[Polymers without energy ray-curable groups (b)] When the energy ray-curable component (a) of the composition (IV-1) and the film for forming an energy ray-curable protective film contains the compound (a2), it may further contain a polymer without an energy ray-curable group (b) is better. At least a part of the polymer (b) may be cross-linked with a cross-linking agent, or may not be cross-linked.

Examples of the polymer (b) system without an energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins. Among these, the polymer (b) is preferably an acrylic polymer (hereinafter also simply referred to as "acrylic polymer (b-1)").

The acrylic polymer (b-1) system may be a well-known product. For example, it may be a single polymer of a single acrylic monomer, or a copolymer of two or more acrylic monomers, or may be composed of one or Copolymers of two or more acrylic monomers and monomers other than one or more acrylic monomers (non-acrylic monomers).

The acrylic monomer constituting the acrylic polymer (b-1) includes, for example, alkyl (meth)acrylate, (meth)acrylate having a cyclic skeleton, and (propylene-containing) ( Methacrylates, hydroxyl-containing (meth)acrylates, substituted amine-containing (meth)acrylates, etc. Here, the so-called "substituted amine group" is as described above.

Examples of the (meth)acrylic acid alkyl ester system include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth) Group) n-butyl acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate Ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (A Group) Tridecyl acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate Esters (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. It is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

Examples of the (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; Aryl (meth)acrylate such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylate such as (cyclopentenyl) (meth)acrylate; (Meth)acrylic acid cyclopentenyloxyalkyl ester and the like.

Examples of the glycidyl group-containing (meth)acrylate system include glycidyl (meth)acrylate. Examples of the above-mentioned hydroxyl-containing (meth)acrylates include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth) Group) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like. Examples of the above-mentioned substituted amine group-containing (meth)acrylate system include N-methylaminoethyl (meth)acrylate.

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

At least a part of the polymer (b) having no energy ray-curable groups after crosslinking with a crosslinking agent may be derived from, for example, the reactive functional group and crosslinking agent in the polymer (b) React to the latter. The above-mentioned reactive functional group system is not particularly limited as long as it is appropriately selected according to the type of crosslinking agent and the like. For example, in the case of a cross-linking agent-based polyisocyanate compound, the reactive functional group may include a hydroxyl group, a carboxyl group, an amine group, and the like. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. In the case of a crosslinking agent-based epoxy compound, the reactive functional group may include a carboxyl group, an amine group, an amide group, and the like. Among these, a carboxyl group having a high reactivity with an epoxy group is preferred. However, from the viewpoint of preventing corrosion of the semiconductor wafer and the circuit of the semiconductor wafer, the reactive functional group is preferably a group other than the carboxyl group.

Examples of the polymer (b) having no reactive energy-curable groups having reactive functional groups include those obtained by polymerizing monomers having at least the reactive functional groups. In the case of the acrylic polymer (b-1), as long as any one or both of the above-mentioned acrylic monomers and non-acrylic monomers listed as monomers constituting it are used, they have the above-mentioned reactive functional group Can. The above-mentioned polymer (b) having a reactive functional group having a hydroxyl group may, for example, be obtained by polymerizing a (meth)acrylate containing a hydroxyl group, and in addition to the above-mentioned ones Among acrylic monomers or non-acrylic monomers, monomers in which one or more hydrogen atoms are substituted with the above-mentioned reactive functional groups are obtained by polymerization.

In the above polymer (b) having a reactive functional group, the amount of structural units derived from the monomer having a reactive functional group relative to the total number of structural units constituting the above polymer (b) having a reactive functional group The ratio (content) is preferably 1-20% by mass, and more preferably 2-10% by mass. When the above ratio is in this range, the degree of crosslinking of the polymer (b) can become a better range.

The weight-average molecular weight (Mw) of the polymer (b) without an energy ray-curable group is preferably from 10,000 to 2,000,000, and more preferably from the viewpoint of making the film-forming property of the composition (IV-1) better. 100000~ 1500000. Here, the "weight average molecular weight" is as described above.

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

The composition (IV-1) may include any one or both of the polymer (a1) and the compound (a2). However, when the composition (IV-1) contains the above-mentioned compound (a2), it is preferable to further contain the polymer (b) without an energy ray-curable group, and in this case, it is also preferable to further contain the above-mentioned (a1 ). In addition, the composition (IV-1) may not contain the above-mentioned compound (a2), but may contain both the above-mentioned polymer (a1) and the polymer (b) having no energy ray-curable group.

When the composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) without an energy ray-curable group, in the composition (IV-1), the compound The content of (a2) is 100 parts by mass relative to the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group, preferably 10 to 400 parts by mass, more preferably 30 to 350 parts Quality parts.

In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of the components other than the solvent (ie, energy ray The total content of the energy ray-curable component (a) and the polymer (b) without an energy ray-curable group in the film for forming a curable protective film) is preferably 5 to 90% by mass, more preferably 10 ~80% by mass, 20~70% by mass of Tejia. By setting the above ratio of the content of the energy ray curable component within such a range, the energy ray curability of the thin film for forming an energy ray curable protective film can be made better.

The composition (IV-1) is in addition to the above-mentioned energy ray-curable components, and the blending purpose may also include thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives. Select one type or two or more types in the group.

For example, by using the above-mentioned composition (IV-1) containing an energy ray-curable component and a thermosetting component, the adhesive force of the formed thin film for forming an energy ray-curable protective film by heating can be improved, And the strength of the protective film formed by the thin film for forming an energy ray-curable protective film is also improved. Furthermore, by using the above-mentioned composition (IV-1) containing the energy ray-curable component and the coloring agent, the formed energy ray-curable protective film-forming film can exhibit the thermosetting protection described above. The same effect is obtained when the film for film formation contains the colorant (I).

The above-mentioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, coloring agents and general-purpose additives of the composition (IV-1) can be exemplified by thermosetting with the composition (III-1) The same as the sexual component (B), the filler (D), the coupling agent (E), the crosslinking agent (F), the photopolymerization initiator (H), the colorant (I), and the general-purpose additive (J).

In the composition (IV-1), the above thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants and general-purpose additives may be used alone or in combination of two or more. If two or more kinds are used together, the combination and ratio system can be arbitrarily selected.

The contents of the above thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants and general additives of the composition (IV-1) may be adjusted as long as they are suitable for the purpose, and No special restrictions.

Since the composition (IV-1) can improve the handling property by dilution, it is preferable to further contain a solvent. The solvent contained in the composition (IV-1) may, for example, be the same solvent as the aforementioned composition (III-1). The solvent system contained in the composition (IV-1) may be only one kind or two or more kinds.

<<Method for manufacturing composition for forming energy beam curable protective film>> The composition for forming an energy ray-curable protective film, such as the composition (IV-1), can be obtained by blending the components that constitute it. The order of addition of each component during blending is not particularly limited, and two or more components may be added simultaneously. When using a solvent, the solvent can be mixed with any of the blended components other than the solvent, and then the blended component can be used after pre-dilution. It can also be used without pre-diluted any of the blended components other than the solvent. , The solvent is mixed with these blending components for use. At the time of blending, the method of mixing the components is not particularly limited, and for example, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves It is appropriately selected from known methods. The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each blending component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15 to 30°C.

○Thin film for forming non-curing protective film Although the thin film for forming a non-curable protective film does not show a characteristic change due to curing, in the present invention, it is considered that a protective film has been formed at the stage of attaching to a target place such as the back surface of a semiconductor wafer.

Preferred films for forming a non-curable protective film include, for example, those containing thermoplastic resin.

<Non-curable protective film forming composition (V-1)> The composition system for forming a non-curable protective film may be, for example, a composition (V-1) for forming a non-curable protective film containing the thermoplastic resin (also referred to as "composition (V-1)" in this specification) Wait.

[Thermoplastic resin] The thermoplastic resin is not particularly limited. Examples of the thermoplastic resin include acrylic resins, polyesters, polyurethanes, phenoxy resins, polybutene, polybutadiene, and polystyrene. Non-curable resins are the same.

The above-mentioned thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio system Can be chosen arbitrarily.

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

The composition (V-1) is not only the above-mentioned thermoplastic resin, but the blending purpose may also contain one or two or more selected from the group consisting of fillers, coupling agents, crosslinking agents, colorants, and general-purpose additives.

For example, by using the above-mentioned composition (V-1) containing a thermoplastic resin and a coloring agent, the formed thin film for forming a non-curable protective film can be shown as described above for forming a thermosetting protective film. The film has the same effect as when the coloring agent (I) is contained.

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

In the composition (V-1), the fillers, coupling agents, crosslinking agents, colorants and general-purpose additives may be used alone or in combination of two or more. If two or more are used in combination, The combination and ratio are optional.

In the composition (V-1), the contents of the filler, coupling agent, crosslinking agent, colorant, and general-purpose additives may be adjusted as long as they are suitable for the purpose, and are not particularly limited.

Since the composition (V-1) is diluted to improve handling properties, it is preferable to further contain a solvent. The solvent contained in the composition (V-1) may, for example, be the same solvent as the aforementioned composition (III-1). The solvent system contained in the composition (V-1) may be only one kind or two or more kinds.

<<Method for manufacturing composition for forming non-curable protective film>> The composition for forming a non-curable protective film such as the composition (V-1) can be obtained by blending the components constituting the same. The order of addition of each component during blending is not particularly limited, and two or more components may be added simultaneously. When using a solvent, the solvent can be mixed with any of the blended components other than the solvent, and then the blended component can be used after pre-dilution. It can also be used without pre-diluted any of the blended components other than the solvent. , The solvent is mixed with these blending components for use. At the time of blending, the method of mixing the components is not particularly limited, and for example, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves It is appropriately selected from known methods. The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each blending component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15 to 30°C.

◎Other layers The above-mentioned support sheet is within the range that does not cause damage and the effects of the present invention. In addition to the base material and the adhesive layer, the intermediate layer and other layers may be provided. In addition, the above-mentioned composite film for forming a protective film is within the scope of not damaging and the effects of the present invention, and may include other layers in addition to the base material, the adhesive layer, and the film for forming a protective film. The layer system may be the above-mentioned other layers included in the support sheet, or may be arranged so as not to directly contact the support sheet. The other layers described above can be arbitrarily selected according to the purpose, and the type is not particularly limited.

An embodiment of the composite sheet for forming the support sheet and the protective film includes, for example, an adhesive layer system which is non-energy ray-curable, and the adhesive layer contains the above-mentioned structural unit derived from at least an alkyl (meth)acrylate. Acrylic polymer and crosslinking agent, in the adhesive layer, the content of the crosslinking agent is 0.3 to 50 parts by mass relative to 100 parts by mass of the acrylic polymer, and the maximum height of the first surface of the substrate Roughness (Rz) is 0.01~8μm.

An embodiment of the composite sheet for forming the support sheet and the protective film includes, for example, an adhesive layer that is non-energy ray-curable, and the adhesive layer contains at least the above-mentioned structural unit derived from an alkyl (meth)acrylate. Acrylic polymer and crosslinking agent, in the adhesive layer, the content of crosslinking agent is 0.3 to 50 parts by mass relative to the content of the acrylic polymer above 100 parts by mass, the above acrylic polymer system has an alkyl carbon The structural units derived from alkyl (meth)acrylates with a number of 4 or more and the structural units derived from hydroxyl-containing monomers, and the maximum height roughness (Rz) of the first surface of the substrate is 0.01 to 8 μm.

An embodiment of the composite sheet for forming the support sheet and the protective film includes, for example, an adhesive layer that is non-energy ray-curable, and the adhesive layer contains at least the above-mentioned structural unit derived from an alkyl (meth)acrylate. Acrylic polymer and crosslinking agent, in the adhesive layer, the content of crosslinking agent is 0.3 to 50 parts by mass relative to the content of the acrylic polymer above 100 parts by mass, the above acrylic polymer system has an alkyl carbon Structural units derived from alkyl (meth)acrylates having a number of 4 or more and structural units derived from hydroxyl-containing monomers, in the above acrylic polymer, relative to the total amount of structural units, derived from hydroxyl-containing monomers The content of the structural unit is 1 to 35% by mass, and the maximum height roughness (Rz) of the first surface of the base material is 0.01 to 8 μm.

One embodiment of the composite sheet for forming the support sheet and the protective film includes, for example, the adhesive layer is non-energy ray-curable and the adhesive layer contains at least the above-mentioned structural units derived from alkyl (meth)acrylate Acrylic polymer and crosslinking agent, in the adhesive layer, the content of crosslinking agent is 0.3 to 50 parts by mass relative to the content of the acrylic polymer above 100 parts by mass, the above acrylic polymer system has an alkyl carbon Structural units derived from alkyl (meth)acrylates having a number of 4 or more and structural units derived from hydroxyl-containing monomers, in the above acrylic polymer, relative to the total amount of structural units, derived from hydroxyl-containing monomers The content of the structural unit is 1 to 35% by mass, the cross-linking agent-based isocyanate-based cross-linking agent, and the maximum height roughness (Rz) of the first surface of the substrate is 0.01 to 8 μm.

◇Manufacturing method of composite sheet for forming protective film The above-mentioned composite film for forming a protective film can be manufactured, for example, by the following manufacturing method (also referred to as "manufacturing method (S1)" in this specification), which includes: in accordance with the order of the substrate, the adhesive layer, and the film for forming a protective film The step of making a laminate formed by stacking in its thickness direction (also referred to as "layer preparation step (1)" in this specification); and the step of storing the above laminate under pressure in its thickness direction (in this specification) (Also called "Layer Preservation Step"). The formation method of each layer (base material, adhesive layer, and protective film forming film) is as described above. Hereinafter, the manufacturing method (S1) will be described in more detail in accordance with each step.

◎Manufacturing method (S1) ＜＜Layer production step (1)＞＞ In the above-mentioned lamination sheet manufacturing step (1), a lamination sheet constructed in the thickness direction in the order of the substrate, the adhesive layer, and the protective film-forming film is produced. In this step, for example, a layered sheet having the same layered structure as the target protective film-forming composite sheet is produced by layering in accordance with the positional relationship of the above layers (base material, adhesive layer, film for forming a protective film, etc.). In addition, in this specification, the "lamination sheet" refers to a person having the same lamination structure as the above-mentioned composite sheet for forming a protective film as described above, and has not yet performed the lamination sheet preservation step as described above.

For example, when manufacturing a support sheet, when an adhesive layer is laminated on a base material, the adhesive composition may be applied on the base material and dried as necessary.

On the other hand, for example, when a film for forming a protective film is further laminated on the adhesive layer that has been laminated on the substrate, the protective film forming composition can be directly formed by applying the protective film forming composition on the adhesive layer Use film. The layer other than the thin film for forming a protective film is also a composition for forming this layer, and this layer can be laminated on the adhesive layer according to the same method. Accordingly, when any one of the compositions is used to form a continuous two-layer laminated structure, a new layer can be formed by further applying the composition to the layer formed by the above composition. However, the layer to be stacked after these two layers is preferably formed in advance on the other release film using the above composition, and then the exposed surface of the formed layer on the opposite side to the side in contact with the release film will have The exposed surface of the remaining layer formed is bonded to form a continuous double-layer build-up structure. In this case, the above composition is preferably applied to the peeling treatment surface of the peeling film. The peeling film can be removed as needed after the layered structure is formed.

For example, when manufacturing an adhesive layer formed by laminating an adhesive layer on a substrate and laminating a protective film forming film on the adhesive layer (a support film is formed by a protective film of a laminate of a substrate and an adhesive layer) When using a composite sheet), apply the adhesive composition on the substrate and dry it if necessary, and laminate the adhesive layer on the substrate and apply the protective film forming composition on the release film and dry it if necessary , And a protective film forming film is formed on the peeling film. Then, the exposed surface of the protective film forming film is bonded to the exposed surface of the adhesive layer that has been laminated on the base material, and the protective film forming film is laminated on the adhesive layer to obtain the above-mentioned laminated sheet.

In addition, when the adhesive layer is laminated on the substrate, as described above, it is also possible to replace the method of applying the adhesive composition on the substrate, instead applying the adhesive composition on the release film, and drying if necessary. An adhesive layer is formed on the peeling film, and then the exposed surface of the layer is bonded to one surface of the substrate to laminate the adhesive layer on the substrate. Regardless of the method, the peeling film can be removed at any timing after the target build-up structure is formed.

Accordingly, the layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method previously formed on the release film and then bonded to the surface of the target layer, so the layer adopting this step is appropriately selected as necessary , The above laminate can be manufactured.

For example, the composite sheet for forming a protective film is usually stored in a state where a peeling film is bonded to the surface of the outermost layer (for example, the film for forming a protective film) opposite to one surface of the support sheet. Therefore, on this peeling film (preferably a peeling treatment surface), a composition for forming a protective film is applied to form a composition that constitutes the outermost layer, and then drying is performed if necessary, and the composition that constitutes the outermost layer is formed on the peeling film Layer, and then the remaining layers are laminated on the exposed surface on the side opposite to the side in contact with the release film of this layer according to any of the above-mentioned methods. Even if the release film is not removed and the bonded state is maintained, the above-mentioned laminated sheet can be obtained.

When the composite sheet for forming a protective film includes the above-mentioned other layers, the step of providing the above-mentioned layers may be appropriately added so as to be an appropriate arrangement position at a suitable timing in the step (1) of the build-up sheet.

The shape of the laminate sheet produced in the laminate sheet production step (1) is not particularly limited. For example, it is possible to produce a long lamination sheet suitable for winding in a roll shape, but it is also possible to produce a lamination sheet of other shapes that are not elongated.

＜＜Layer storage procedure＞＞ In the lamination sheet storage step, the lamination sheet is stored in a state of being pressed in its thickness direction. In this step, the method of storing the laminated sheet under a pressurized state may include, for example, rolling a long length of the laminated sheet into a roll shape, and maintaining the wound laminated sheet in a state of The method of taking the generated pressure and applying it on one or both sides of the laminate; storing the laminate without winding the elongated laminate in a roll shape, or maintaining the unfolded laminate, or the non-strip The laminated sheet is stored under pressure on one side or both sides.

When winding the long laminated sheet into a roll shape, it is better to wind the laminated sheet toward the long side. When winding the laminate, for example, the winding tension is preferably 150 to 170 N/m, the winding speed is preferably 45 to 55 m/min, and the tapering ratio (decrease rate) of the winding tension is preferably 85 ~95%. By adopting such winding conditions, it is possible to pressurize and store the laminated sheet with more appropriate pressure. Such winding conditions are particularly suitable for laminates with a thickness of 100 to 300 μm, a width of 300 to 500 mm, and a length of 40 to 60 m, but the size of the laminate is not limited to this.

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

The laminated sheet system wound in the form of a roll can be stored at normal temperature or room temperature, but it is preferably stored under heating. By performing heat and pressure storage in this way, the buildability between the adhesive layer and the protective film forming film, and the protective film or protective film forming film can be obtained with a more excellent visibility of marking through the support sheet. Use composite tablets.

When winding the laminated sheet in a roll shape, the heating temperature during 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 in a roll is not particularly limited, but it is preferably 24 to 720 hours (1 to 30 days), more preferably 48 to 480 hours (2 to 20 days), and especially good 72~240 hours (3~10 days).

The laminated sheet wound in the form of a roll may, for example, process a film for forming a protective film and a support sheet into a specific shape, and then process a plurality of laminates of the film for forming a supporting sheet and a protective film processed in accordance therewith before it is protected One side of the film-forming film is attached to the long release film, and at the same time, the longitudinal direction of the release film is neatly arranged. In this case, the thin film for forming a protective film preferably has the same or almost the same planar shape (usually a circular shape) as the semiconductor wafer. In addition, the support piece in this case preferably has the same or nearly the same outer shape as the jig for fixing the support piece in the cutting device. Moreover, in this case, it is preferable to provide a strip-shaped sheet in the vicinity of the peripheral edge portion in the short-side direction of the laminate bonding surface of the release film so as not to overlap the laminate. This belt-shaped sheet is used to suppress the difference in height of the surface of the layered product (also referred to as "layer mark" in this specification) when the layered sheet is wound in a roll shape. The above-mentioned lamination marks are due to the fact that the lamination position of the laminate (the laminate of the processed support sheet and the film for forming a protective film) in the lamination sheet reel does not match in the radial direction of the reel, resulting in the application of high pressure on the surface of the lamination article Cause. If the belt-shaped sheet is provided near the peripheral edge portion, such a high pressure is not applied to the surface of the laminate, and the occurrence of the laminate mark is suppressed.

When the long laminated sheet is not wound in a roll shape and is unfolded, and when the laminated sheet is not a long sheet, it is better to store the plural laminated sheets in a further layer. However, when stacking the laminate sheets in this manner, it is preferable that the direction of the plurality of laminate sheets and the position of the peripheral portion are aligned with each other.

The shape and size of the non-long lamination sheet (in other words, monolithic lamination sheet) are not particularly limited. For example, it is preferable to use a dicing device, and adjust the shape and size of the lamination sheet according to the shape and size of the semiconductor wafer and the shape and size of the jig for fixing the support piece in the dicing device according to a method suitable for processing a single semiconductor wafer .

The above-mentioned laminated sheet system in a laminated state can be stored at normal temperature or room temperature, but it is preferably stored under heating. By performing heat and pressure storage in this way, the buildability between the adhesive layer and the protective film forming film, and the protective film or protective film forming film can be obtained with a more excellent visibility of marking through the support sheet. Use composite tablets. Furthermore, when the laminated sheet in the laminated state is subjected to pressure storage, both the heating temperature and the storage time can be set to be the same as when the laminated sheet is wound in a roll shape.

In the manufacturing method (S1), after the step of storing the laminated sheet is completed, by releasing the pressure of the laminated sheet and optionally heating, the target composite film for forming a protective film can be obtained.

In the manufacturing method (S1) of the laminated sheet manufacturing step (1), the order of laminating (laminating) the base material, adhesive layer, and protective film forming film is not particularly limited. Laminating adhesive layer), making a film for forming a protective film in advance, and laminating a film for forming a protective film on a support sheet, either or both of the supporting sheet and the film for forming a protective film before laminating it, Separately, pressurized storage was carried out in the same manner as in the case of the above laminated sheet. By separately storing the supporting sheet before lamination under pressure, it is possible to more effectively suppress the occurrence of the above-mentioned unbonded area between the base material and the adhesive layer. In addition, by separately storing the film for protective film formation before lamination under pressure, the unevenness (increased smoothness) of the surface (second surface) of the film for protective film formation and the protective film adjacent to the adhesive layer can be reduced, To enhance the design of the protective film forming film and protective film.

That is, the above-mentioned composite film for forming a protective film can also be manufactured by, for example, the following manufacturing method (also referred to as "manufacturing method (S2)" in this specification), which includes: a support sheet on which a base material and an adhesive layer have been laminated The step of laminating a film for forming a protective film on the above-mentioned adhesive layer to produce a laminated sheet formed by laminating the substrate, the adhesive layer, and the film for forming a protective film in its thickness direction (also referred to as "laminating sheet production" in this specification) Step (2)"); and the step of storing the laminated sheet under pressure in its thickness direction (storing step); wherein, before the laminated sheet manufacturing step (2) (that is, the supporting sheet and the protection are laminated (Before the film for film formation), further including: a step of applying pressure and storing one or both of the above-mentioned support sheet and the film for forming a protective film in the thickness direction (in this specification, the step of storing the support sheet is referred to as The "support sheet storage step" refers to the step of storing the protective film forming thin film as the "protective film forming thin film storing step").

◎Manufacturing method (S2) The above-mentioned manufacturing method (S2) is in addition to the above-mentioned build-up sheet manufacturing step (1) is to perform the build-up sheet manufacturing step (2), in addition to performing either or both of the above-mentioned support sheet storage step and protective film forming film storage step It is the same as the above-mentioned manufacturing method (S1).

＜＜Layer production step (2)＞＞ The above-mentioned lamination sheet manufacturing step (2), as described above, except for the preparation of a support sheet in advance, the preparation of a thin film for forming a protective film in advance, and the limitation of the lamination order of each layer in the manner of laminating the thin film for forming a protective film on the support sheet, and the manufacturing method The production step (1) of the laminated sheet of (S1) is the same.

＜<Supporting sheet storage step, protective film forming film storage step>＞ The above-mentioned support sheet storage step and the protective film formation film storage step are the respective storage objects other than the laminate sheet but the support sheet or the protective film formation film, which can be carried out in the same manner as in the production method (S1) of the laminate sheet storage step get on. In this case, for example, the storage time of the thin film for forming the support sheet and the protective film is the same as the case of the laminated sheet, and can be independently set to 24 to 720 hours (1 to 30 days) and 48 to 480 hours (2 to 20 days, respectively) ) And 72 to 240 hours (3 to 10 days).

On the other hand, the above support sheet storage step and the protective film formation film storage step are the same as described above, in addition to changing the storage target, there is also a change in the storage target object (support sheet or protective film forming film) storage time, in addition to these Except for the change, it is carried out in the same manner as the lamination sheet storage step of the manufacturing method (S1). In this case, for example, the storage time of the support sheet and the protective film forming film can be independently set to 12 to 720 hours (0.5 to 30 days), 12 to 480 hours (0.5 to 20 days), and 12 to 240 hours ( 0.5~10 days). However, this is only an example of the above-mentioned storage time.

The manufacturing method of the supporting sheet of the present invention includes the following steps: Preparing a first laminated sheet including a base material, an adhesive layer, and a first release film in this order, and the base material has an uneven surface on one surface of the adhesive layer; and The first laminated sheet is stored at 53 to 75°C for 24 to 720 hours.

Furthermore, the method for manufacturing a composite film for forming a protective film according to another aspect of the present invention includes the following steps: Prepare a first laminate sheet and a laminate film. The first laminate sheet includes a substrate, an adhesive layer, and a first release film in sequence. The substrate has a concave-convex surface on one surface of the adhesive layer. The laminate film includes a first 3 The peeling film, the film for forming the protective film and the second peeling film; Store the first laminated sheet at 53~75℃ for 24~720 hours; The first peeling film and the second peeling film are removed, the exposed surface of the adhesive layer is bonded to the exposed surface of the protective film forming film, and the manufacturing sequence includes the substrate, the adhesive layer, and the protective film Forming film and the second lamination sheet of the above-mentioned third release film; and The above second laminated sheet is stored at 53 to 75°C for 24 to 720 hours.

Furthermore, another aspect of the present invention relates to a method for manufacturing the protective film-forming composite sheet, wherein the step of bonding the exposed surface of the adhesive layer to the exposed surface of the protective film-forming film is at 53 ~75°C, press under pressure of 0.3~0.8MPa.

Furthermore, another aspect of the present invention relates to a method for manufacturing the protective film-forming composite sheet, wherein the first laminate sheet, the laminate film, and the second laminate sheet are each a long laminate sheet or laminate film; The first laminate sheet and the second laminate sheet are respectively wound and stored in a roll shape in the storage step. [Example]

Hereinafter, the present invention will be described in more detail using specific embodiments. However, the present invention is not limited to the embodiments shown below.

<Manufacture raw materials of the composition for forming a protective film> The raw materials used for the production of the protective film forming composition are as follows. ‧Polymer composition (A) (A)-1: Acrylic polymer formed by copolymerization of methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) (weight average molecular weight 370,000, glass transition temperature 6°C) ‧Thermosetting component (B1) (B1)-1: Bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184~194g/eq) (B1)-2: Bisphenol A epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800-900g/eq) (B1)-3: Dicyclopentadiene type epoxy resin ("Epicron HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 255~260g/eq) ‧Heat hardener (B2) (B2)-1: Dicyandiamide ("ADK HARDENER EH-3636AS" manufactured by ADEKA Corporation, thermally active latent epoxy resin hardener, (thermally active latent) active hydrogen content 21g/eq) ‧Hardening accelerator (C) (C)-1: 2-phenyl-4,5-dimethylolimidazole ("Curezol 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) ‧Filler (D) (D)-1: Silicon dioxide filler ("SC2050MA" manufactured by Admatechs, surface-modified silica filler with epoxy compound, average particle size 0.5 μm) ‧Coupling agent (E) (E)-1: 3-aminopropyltrimethoxysilane ("A-1110" manufactured by NUC Corporation) ‧Colorant (I) (I)-1: Black pigment (manufactured by Dari Fine Chemicals)

[Example 1] ＜Manufacture of support sheet＞ (Manufacture of adhesive composition (I-4)) Manufacture of a non-energy ray-curable adhesive composition (I-4) with a solid content concentration of 30% by mass, which contains an acrylic polymer (100 parts by mass, solid content) and trifunctional xylylene diisocyanate It is a cross-linking agent ("TAKENATE D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)) and also contains a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate as a solvent. The above-mentioned acrylic polymerization system has a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass). Copolymer.

(Manufacture of support sheet) The first peeling film (“SP-PET381031” manufactured by Lintec Corporation, thickness 38 μm) on one side of which a polyethylene terephthalate film was subjected to peeling treatment on one side by polysiloxane treatment, on the peeling treatment surface, The adhesive composition (I-4) obtained above was applied and heated and dried at 120° C. for 2 minutes to form a non-energy ray-curable adhesive layer. At this time, the conditions were set so that the thickness of the adhesive layer became 4 μm, and the adhesive composition (I-4) was applied.

On one surface of a polypropylene film (made by Mitsubishi Resin Co., Ltd., thickness 80 μm), the uneven surface of the metal roller is rotated while being heated to press, whereby one of the surfaces is an uneven surface and the other surface is a smooth surface (Glossy surface) base material. For the uneven surface of this substrate, the maximum height roughness (Rz) was measured according to JIS B 0601:2013, and the result was 5 μm.

Next, by bonding the concave-convex surface of the base material on the exposed surface of the obtained adhesive layer, a first laminated sheet laminated in the thickness direction of the base material, the adhesive layer, and the first release film was obtained. The width of the obtained first laminate sheet (in other words, the width of the base material and the adhesive layer) was 400 mm, and the length was 250 m.

Next, take the first laminate with the overall size of 400 mm × 250 m obtained as described above, and set its long-side direction as the winding direction. At the winding tension of 160 N/m, the winding speed of 50 m/min, and the winding tension tapering ratio Under 90% of the conditions, it is wound around an ABS resin core with an outer diameter of 88 mm, and the winding takes the form of a roll. At this time, the first laminate sheet was wound so that the base material faced outward in the radial direction of the roller (in other words, the first release film was brought into contact with the core). Next, this roll-shaped first laminated sheet was stored in an air environment at a temperature of 60°C for 7 days (168 hours). The support sheet was obtained as described above. For this support sheet, the evaluation of the unattached area between the base material and the adhesive layer described later can be immediately performed. In addition, this support sheet is used for the production of a composite sheet for forming a protective film described later.

<Manufacture of composite sheet for forming protective film> (Manufacture of the 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), hardening accelerator (C)-1 (2 parts by mass), filler (D)-1 (320 parts by mass), coupling agent (E)-1 (2 parts by mass) Parts) and coloring agent (I)-1 (18 parts by mass), dissolved or dispersed in a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate, and stirred at 23°C to obtain a thermosetting property with a solid content concentration of 51% by mass Composition for forming a protective film (III-1). In addition, all the blending amounts shown here refer to "solid content".

(Manufacture of thin film for forming protective film) Using a polyethylene terephthalate film with one side peeled by polysiloxane treatment and subjected to a peeling treatment (third peeling film, "SP-PET381031" manufactured by Lintec, thickness 38 μm), on the peeling treatment surface The composition (III-1) for forming a protective film obtained above was applied using a knife coater, and dried at 100° C. for 2 minutes to obtain a thermosetting film for forming a protective film with a thickness of 25 μm.

In addition, the obtained protective film forming film was not provided with an exposed surface on one side of the third release film, and a release film (second release film, "SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) was peeled. By treating the surface, a laminated film in which the second release film is provided on one side of the protective film forming film and the third release film is provided on the other side is obtained. The width of the obtained laminated film (in other words, the widths of the protective film forming film, the second release film, and the third release film) was 400 mm.

(Manufacture of composite sheet for forming protective film) Prepare a set of 2 rollers with a diameter of 5 cm and a depth up to 3 mm from the surface consisting of heat-resistant silicone rubber with a hardness of 50 degrees. The first release film is removed from the adhesive layer of the support sheet obtained above. In addition, the second release film was removed from the laminated film obtained above. Then, the exposed surface of the adhesive layer formed by removing the first release film is opposed to the exposed surface of the film for forming a protective film formed by removing the second release film, and the support sheet and the film for forming a protective film are made Overlay to form a laminate, while passing the laminate at a speed of 0.3 m/min through the gap between these rollers whose temperature is set at 60°C, and applying heat pressing (heat lamination) at a pressure of 0.5 MPa. In this way, a second laminated sheet having the same lamination structure as the target protective film-forming composite sheet is formed by laminating the substrate, the adhesive layer, the protective film forming film, and the third release film in the thickness direction in this order. (Composite sheet for forming a protective film before storage). The width of the obtained second laminate sheet (in other words, the width of the support sheet) was 400 mm.

Next, the second laminated sheet having the overall size of 400 mm×250 m obtained as described above is set with the longitudinal direction as the winding direction. At the winding tension of 160 N/m, the winding speed of 50 m/min, and the winding tension gradually Under the condition of 90% reduction ratio, it is wound around the core of ABS resin, and the winding takes the form of a roll. At this time, the second laminate sheet is wound up so that the base material faces outward in the radial direction of the roller (in other words, the third release film is brought into contact with the core). Next, the roll-shaped second laminate sheet was stored in an air environment at 60°C for 7 days (168 hours). As described above, the composite sheet for forming a protective film of the present invention having the structure shown in FIG. 2 was obtained.

Next, the composite sheet for forming a protective film of the present invention after completion of storage under such heat and pressure conditions was evaluated for the items shown below.

<Evaluation of composite sheet for forming support sheet and protective film> (Evaluation of the presence of unlaminated areas between the substrate and the adhesive layer and the distance between the layers) From 5 places of the obtained composite film for forming a protective film, a test piece having a size of 3 mm×3 mm was cut out. The cut positions of these five places are set to correspond to one place in the center of the thin film for forming a circular protective film, and four places close to the peripheral part and almost point-symmetrical with respect to the center. Among these five places, the cutting distance is equivalent to one place in the center, and the distance between the centers of the other four places close to the periphery is 100 mm.

Using a cross-section sample preparation device ("Section Polishing Machine SM-09010" manufactured by JEOL), the conditions of the intermittent gate were set to "in" for 10 seconds and "out" for 5 seconds, the ion source voltage was set to 3 kV, and the total polishing time was set For 24 hours, a cross section was formed from the above test piece. The newly formed cross-section is assumed to have only one surface per test piece.

Using a scanning electron microscope (SEM), the newly formed cross-sections of these five test pieces were observed to confirm whether there were unbonded areas between the substrate and the adhesive layer. Then, when there is an unlaminated area, the number and the maximum distance between layers (d1) are measured. The cross-sectional observation area of the test piece at this time was defined as an area 1 mm from the center in the width direction of the cross section (in other words, an area of 1 mm in the width direction centered on the midpoints of the two end portions in the width direction of the cross section). In addition, when measuring this interlayer distance, a cross-section was formed in the composite sheet for forming a protective film in the same way as the above test piece, and the maximum value (d1) of the interlayer distance between the substrate and the adhesive layer was measured at this cross-section. Then, in accordance with the following criteria, evaluation was performed on the unlaminated area between the substrate and the adhesive layer. The results are shown in Table 1.

(Evaluation of the number of unattached areas) A: The number of unattached areas is less than 5. B: The number of unattached areas is 6-9. C: The number of unattached areas is more than 10.

(Evaluation of the maximum distance (d1) between layers) A: There is no unbonded area at all, or the maximum value (d1) between the layers is less than 0.1 μm. B: Although there is an unlaminated area, the maximum interlayer distance (d1) is 0.1 to 0.5 μm. C: There is an unlaminated area, and the maximum value (d1) of the interlayer distance is greater than 0.5 μm.

(Evaluation of printability of protective film) Remove the third release film from the composite film for forming a protective film obtained above, and attach the exposed surface (the surface opposite to the adhesive layer side) of the film for forming a protective film thus formed to an 8-inch semiconductor The back of the wafer. The attachment at this time was performed using a film laminator ("RAD2700" manufactured by Lintec). In this way, a first layered structure is formed in which the substrate, the adhesive layer, the thin film for forming a protective film, and the semiconductor wafer are stacked in the thickness direction in this order.

Next, using a laser marking device ("CSM300M" manufactured by EO TECHNICS), by irradiating the laser through the support sheet on one side (second side) of the protective film-forming film in the first build-up structure Marking is performed by shooting light. At this moment, 0.3mm×0.2mm size text is printed.

Next, the marking (laser marking) of the protective film forming film was visually observed through the support sheet, and the visibility of the marking (character) was evaluated according to the following criteria. The results are shown in Table 1. The marking visibility of the protective film forming film evaluated here is regarded as equivalent to the marking visibility of the protective film. A: The marking is clear and easy to inspect. B: The marking is slightly blurred and cannot be easily checked. C: The marking is not clear and cannot be inspected.

Next, the support sheet (base material and adhesive layer) is torn off from the protective film forming film. Then, using an optical microscope (manufactured by KEYENCE), the line thickness of the marking (character) formed on the protective film forming film was measured. As a result, the line thickness is over 40 μm, and it is clearly marked.

(Evaluation of the adhesion between the substrate and the adhesive layer) According to JIS K 5600-5-6, using a rotary cutter, a 100 mm square of 1 mm square grid was provided on the adhesive layer of the support sheet, and an adhesive tape (made by Cello tape [NICHIBAN Co., Ltd.] , Registered trademark]), tear the adhesive tape at an angle of about 60°, 0.5 seconds to 1.0 seconds, count the number of small squares remaining in the 100 small squares, and then test the adhesion between the substrate and the adhesive layer . The adhesion evaluation was carried out in accordance with the following criteria. Then, the evaluation of the adhesion between the base material and the adhesive layer was performed in accordance with the following criteria. The results are shown in Table 1. A: The number of remaining small squares is more than 90. B: The number of remaining small squares is more than 70 and less than 90. C: The number of remaining small squares is less than 70.

<Manufacture of composite sheet for forming support sheet and protective film, and evaluation of composite sheet for forming support sheet and protective film> [Example 2] The same method as in Example 1 was followed except that in Example 1, the support sheet wound in the form of a roll was wound and allowed to stand for 3 days (72 hours) under an air environment at a temperature of 60°C. Manufacturing support sheet. Then, the relevant evaluation of the unlaminated area between the base material and the adhesive layer is performed. Then, except for using this support sheet, a composite sheet for forming a protective film was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3] The same method as in Example 1 was followed except that in Example 1, the support sheet wound in the form of a roll was wound and allowed to stand for 1 day (24 hours) under an air environment at a temperature of 60°C. Manufacturing support sheet. Then, the relevant evaluation of the unlaminated area between the base material and the adhesive layer is performed. Then, except for using this support sheet, a composite sheet for forming a protective film was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1] The same method as in Example 1 was followed except that in Example 1, the support sheet wound in the form of a roll was wound and allowed to stand for 1 day (24 hours) under an air environment at a temperature of 50°C. Manufacturing support sheet. Then, the relevant evaluation of the unlaminated area between the base material and the adhesive layer is performed. Then, except for using this support sheet, a composite sheet for forming a protective film was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2] In the case of Example 1, the relevant evaluation of the unlaminated area between the base material and the adhesive layer was immediately performed on the winding-up support sheet. Then, except for using this support sheet, a composite sheet for forming a protective film was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 3] In the case of Example 1, the relevant evaluation of the unlaminated area between the base material and the adhesive layer was immediately performed on the winding-up support sheet. In addition, the support sheet is used for the subsequent manufacture of a composite sheet for forming a protective film. Then, a thin film for protective film formation was produced in the same manner as in Example 1, except that the step of heating and pressing (heating lamination) was not performed, and a composite sheet for protective film formation was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Then, except using such a support sheet, in the same manner as in Example 1, a composite sheet for forming a protective film was produced and evaluated. The results are shown in Table 1.

[Table 1]

It is known from the above results that in Examples 1 to 3, the number of unlaminated regions between the substrate and the adhesive layer is 5 or less, and the maximum value (d1) of the interlayer distance is 0.5 μm or less, and a protective film and a protective film are formed The engraving of the support sheet through the film is excellent in visibility, and the good adhesion between the substrate and the adhesive is also good.

In contrast, in Comparative Example 1, although the number of unlaminated regions between the substrate and the adhesive layer is 5 or less, the maximum interlayer distance (d1) exceeds 0.5 μm (0.52 μm), while in Comparative Example 2~ 3. The unlaminated area between the base material and the adhesive layer is more than 6 (8~10), and the maximum distance between the layers (d1) exceeds 0.5μm (0.52~0.9μm), which is between the base material and the adhesive Insufficient adhesion. Also, the protective film and the film for forming a protective film are inferior in visibility through the support sheet. (Industry availability)

The invention can be used in the manufacture of semiconductor devices.

1A, 1B, 1C‧‧‧‧Composite sheet for forming a protective film 10‧‧‧Support sheet 10a‧‧‧Support sheet near one side of the film for forming a protective film (1st side) 10b‧‧‧Support sheet is formed with a protective film The side opposite to the film side (second side) 11‧‧‧ base material 11a‧‧‧ the surface of the base material adjacent to the adhesive layer (first surface, uneven surface) 11b‧‧‧ base material and the adhesive layer The side opposite to the side (second side) 12‧‧‧‧adhesive layer 12a‧‧‧The opposite side of the adhesive layer from the substrate side (first side) 12b‧‧‧The adhesive layer is close to the substrate One side (second side) 13,23‧‧‧Protective film forming film 13a‧‧‧Protective film forming film side opposite to the adhesive layer side (first side) 13b‧‧‧Protective film forming One side of the adhesive layer with the film (second side) 15‧‧‧ Peeling film 16‧‧‧ Adhesive layer for jig 16a‧‧‧ The adhesive layer for jig does not touch one side of the film for protective film formation 23b‧‧ ‧One side of the adhesive layer for forming the protective film (second side) 91,92 ‧‧‧Not bonded area d1‧‧‧Maximum interlayer distance between the base material layer and the adhesive layer T _a ‧‧‧ Layer thickness T _a1 ‧‧‧Minimum adhesive layer thickness T _a2 ‧‧‧Maximum adhesive layer thickness

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

1A‧‧‧Composite sheet for forming protective film

10‧‧‧support sheet

10a‧‧‧One side of the film for forming the protective film on the protective film (the first side)

10b‧‧‧The surface of the support sheet opposite to the side of the protective film forming film (second surface)

11‧‧‧ Base material

11a‧‧‧One side of the substrate adjacent to the adhesive layer (the first side, uneven surface)

11b‧‧‧The surface of the substrate opposite to the adhesive layer side (second surface)

12‧‧‧Adhesive layer

12a‧‧‧The surface of the adhesive layer opposite to the base material side (the first surface)

12b‧‧‧Adhesive layer on the side of the substrate (2nd side)

13‧‧‧Protective film forming film

13a‧‧‧The surface opposite to the adhesive layer side of the film for forming a protective film (the first surface)

13b‧‧‧ One side of the adhesive layer for forming the protective film (second side)

15‧‧‧ peel film

16‧‧‧Adhesive layer for jig

16a‧‧‧The adhesive layer for the jig does not touch one side of the protective film forming film

Claims (8)

A support sheet includes a substrate, and a support sheet provided with an adhesive layer on the substrate, wherein, The above-mentioned base material has a concave-convex surface by one surface of the above-mentioned adhesive layer, When the test piece was cut out from 5 places of the above-mentioned support sheet and the cross-section of the adhesive layer was observed with respect to these 5 test pieces, the maximum value (d1) of the interlayer distance between the base material and the adhesive layer was 0.5 μm or less. For example, in the support sheet of claim 1, the adhesive layer directly contacts the uneven surface of the substrate. For example, the support sheet according to item 1 or 2 of the patent application scope, in which the test piece is cut out from 5 places of the above support sheet, and the cross section of the adhesive layer is observed for the 5 test pieces, the base material and the adhesive layer The number of non-laminated areas is that when the above test pieces are observed in a 1 mm area in the center of the width direction of the cross section of the test pieces, the total number of each test piece is 5 or less. A method for manufacturing a support sheet is a method for manufacturing a support sheet according to any one of the items 1 to 3 of the patent application, including the following steps: Preparing a first laminated sheet including a base material, an adhesive layer and a first release film in sequence, and the base material has a concave-convex surface on one surface of the adhesive layer; and The first laminated sheet is stored at 53 to 75°C for 24 to 720 hours. A composite film for forming a protective film is provided with a film for forming a protective film on the adhesive layer in the supporting sheet according to any one of claims 1 to 3. A method for manufacturing a composite sheet for forming a protective film is a method for manufacturing a composite sheet for forming a protective film, which includes the following steps: Prepare a first laminate sheet and a laminate film, the laminate film including a third release film, a film for forming a protective film, and a second release film in sequence, the first laminate film includes a substrate, an adhesive layer, and a first release film in sequence , And the base material is a concave and convex surface by one surface of the adhesive layer; Store the first laminated sheet at 53~75℃ for 24~720 hours; The first peeling film and the second peeling film are removed, and the exposed surface of the adhesive layer is bonded to the exposed surface of the protective film forming film, and the manufacturing sequence includes the substrate, the adhesive layer, and the protective film Forming film and the second lamination sheet of the above-mentioned third release film; and The above second laminated sheet is stored at 53 to 75°C for 24 to 720 hours. For example, the method for manufacturing a composite film for forming a protective film according to item 6 of the patent application scope, wherein the step of bonding the exposed surface of the adhesive layer to the exposed surface of the protective film forming film is at 53 to 75°C , It is carried out under the pressure state of 0.3~0.8MPa. A manufacturing method according to item 6 or 7 of the patent application scope, wherein the first lamination sheet, the lamination film and the second lamination sheet are each a long lamination sheet or a lamination film; the first lamination sheet and the second The laminated sheets are wound and stored in a roll shape in the above-mentioned storing step.

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