TWI783131B - Composite sheet for forming protective film - 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, and when 3 mm by 3 mm test pieces are cut from five locations on the supporting sheet and the minimum and maximum thicknesses of each of the adhesive layers are measured, the ratio of the average maximum value (L value) to the average minimum value (S value) (L value/S value) is 1.2 or more and less than 5.0. A composite sheet for forming a protective film includes a film for forming the protective film on the adhesive layer in the supporting sheet.

Description

Composite sheet for protective film formation

The present invention relates to a support sheet and a composite sheet for forming a protective film.

In recent years, semiconductor devices have been manufactured using a mounting method known as a "face down method". The inverted method uses a semiconductor wafer with electrodes such as bumps on the circuit surface, and the electrodes are bonded to the substrate. Therefore, the opposite surface of one of the two sides of the semiconductor wafer on which the circuit is provided is exposed.

A resin film containing an organic material used as a protective film is formed on the back surface of the bare semiconductor chip, and then assembled in a semiconductor device in the form of a semiconductor chip with a protective film. The protective film is used to prevent cracking of the semiconductor wafer after dicing and packaging.

Such a protective film is formed, for example, by curing a thin film for forming a curable protective film. Moreover, the film for non-curable protective film formation whose physical properties were adjusted can also be used as a protective film as it is. Therefore, the thin film for protective film formation is used for sticking on the back surface of a semiconductor wafer. For example, the film for forming a protective film is attached to the back of the semiconductor wafer in the state of a composite sheet for forming a protective film integrated with the support used in semiconductor wafer processing, or it is not integrated with the support. Attached to the back of the semiconductor wafer in the melted state.

The composite sheet for forming a protective film is attached to the back of the semiconductor wafer by using the film for forming a protective film, and then it is carried out in an appropriate sequence. Cutting of the protective film, dividing (cutting) the semiconductor wafer into semiconductor wafers, and picking up the semiconductor wafer with the film for forming the protective film after cutting or the protective film on the back from the support sheet (the semiconductor wafer with the thin film for forming the protective film or the semiconductor wafer with the protective film protective film for semiconductor wafers), etc. And, when picking up the semiconductor wafer with the thin film for forming a protective film, the semiconductor wafer with a protective film is formed by curing of the thin film for forming a protective film, and finally a semiconductor device is manufactured using the semiconductor wafer with a protective film. According to this, the support sheet in the composite sheet for protective film formation can be utilized as a dicing sheet. In addition, when the thin film for protective film formation is non-curable, in each of these steps, the thin film for protective film formation is used as it is as a protective film.

On the other hand, after the film for forming a protective film is attached to the back surface of the semiconductor wafer without being integrated with the support sheet, on both sides of the film for forming a protective film, on the side opposite to the surface to which the semiconductor wafer is attached, A support sheet is pasted on 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 by the same method as the above-mentioned case of using the composite sheet for forming a protective film, and a semiconductor device is manufactured. In this case, the film for forming a protective film is attached to the back surface of the semiconductor wafer without being integrated with the support sheet, but the composite sheet for forming a protective film is formed by being integrated with the attached support sheet .

For such a composite sheet for forming a protective film, there is disclosed, for example, a dicing tape-integrated film for protecting the back of a semiconductor, which is a dicing tape comprising a dicing tape (support sheet) and a film for protecting the back of a semiconductor (film for forming a protective film). A film for protecting the back surface of a bulk semiconductor (composite sheet for forming a protective film), and the dicing tape (support sheet) has: a substrate having a concave-convex processed surface, and an adhesive layer laminated on the concave-convex processed surface of the substrate The film for protecting the semiconductor back surface (film for forming a protective film) is laminated on the adhesive layer of the dicing tape; wherein, the haze of the above-mentioned dicing tape is 45% or less (refer to Patent Document 1).

However, in the composite sheet for forming a protective film (the film for protecting the back surface of a semiconductor integrated with dicing tape) disclosed in Patent Document 1, since the adhesive layer is laminated on the uneven surface of the base material, the adhesive cannot sufficiently follow the substrate. The unevenness of the material will cause peeling between the base material and the adhesive. In addition, marking may be performed by laser irradiation on one side of the adhesive layer of the protective film or the film for protective film formation, but the thickness of the adhesive layer is not uniform, and there may be gaps at the thicker portion of the adhesive layer. When the marking visibility through the base material and the adhesive layer is reduced. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 5432853

(Problem to be solved by the invention)

The object of the present invention is to provide a support sheet and a composite sheet for forming a protective film including the above-mentioned support sheet. In the composite sheet for forming a protective film, good adhesion between the base material and the adhesive layer, and good marking visibility of the protective film or film for forming a protective film through the support sheet can be realized. (Technical means to solve the problem)

The supporting sheet provided by the present invention is a supporting sheet comprising a base material, and an adhesive layer is provided on the above-mentioned base material, wherein, the surface of the above-mentioned base material facing the above-mentioned adhesive layer is a concave-convex surface; Cut test pieces from 5 places, and calculate the minimum value and maximum value of the adhesive layer thickness for these 5 test pieces, the ratio of the average value of the above maximum value to the average value of the above minimum value is 1.2 or more and less than 1.2 5.0.

In the support sheet of the present invention, the adhesive layer may also be in direct contact with the concave-convex surface of the substrate. Furthermore, in the composite sheet for forming a protective film provided by the present invention, a thin film for forming a protective film is provided on the adhesive layer in the support sheet. [Invention effect]

By constituting the protective film-forming composite sheet 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 protective film-forming film through the support sheet can be realized.

◇Composite sheet for support sheet and protective film formation A support sheet according to an embodiment of the present invention is a support sheet comprising a substrate and an adhesive layer is provided on the substrate, wherein the surface of the substrate facing the adhesive layer is a concave-convex surface; from the support sheet When the test pieces are cut from 5 places in the test piece, and the minimum value and maximum value of the thickness of the adhesive layer are calculated for these 5 test pieces, the average value of the above maximum value (in this specification, sometimes called "L value") is relatively The ratio (L value/S value) of the average value (in this specification, sometimes referred to as "S value") of the above-mentioned minimum value is 1.2 or more and less than 5.0. Furthermore, in the composite sheet for forming a protective film according to one embodiment of the present invention, a thin film for forming a protective film is provided on the adhesive layer in the support sheet.

The above-mentioned support sheet is provided with an adhesive layer on the concave-convex surface side of the substrate, and the composite sheet for forming a protective film including this support sheet will fully follow the concave-convex surface of the substrate, and the gap between the substrate and the adhesive layer will be suppressed. the stripping situation. More specifically, when the ratio of the L value of the adhesive layer to the S value of the adhesive layer (L value/S value) is 1.2 or more, since the adhesive layer sufficiently follows the unevenness of the base material, the base material There will be no peeling between the adhesive layer and the adhesion between the base material and the adhesive layer. On the other hand, when the ratio of the L value of the adhesive layer to the S value of the adhesive layer (L value/S value) is less than 5.0, the marking inspection of the protective film or protective film forming film through the support sheet Sex was good.

The said test piece was cut out from 5 places of a support sheet, and it cut|disconnected the whole support sheet in the thickness direction. The test piece consists of small pieces that make up all the layers of the support piece.

The size of the test piece is not particularly limited, but it is preferable that the length of one side of the laminated layer or the exposed surface of each layer (substrate, adhesive layer, etc.) constituting the test piece is 2 mm or more. By using a test piece 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, the length of one side is preferably 10 mm or less from the viewpoint of easiness of test piece preparation.

The planar shape of the test piece—that is, the shape of the laminated surface or exposed surface of each layer (substrate, adhesive layer, etc.) that constitutes the test piece is preferably a polygonal shape, and it is more preferably a quadrilateral shape from the viewpoint of easier cutting of the test piece shape.

The test piece is preferably, for example, the laminated surface or the exposed surface of each layer (substrate, adhesive layer, etc.) constituting the test piece is in a quadrangular shape of 3mm×3mm. However, this is only an example of a preferred test piece.

There are no special restrictions on the cutting position of the support sheet in the 5 places of the test piece. In order to obtain the S value and L value of the adhesive layer with higher accuracy, it can be done after considering the predetermined lamination position of the protective film forming film described later. choose. For example, among the planned lamination positions of one film for forming a protective film, select a place belonging to the center (centre of gravity) of the film for forming a protective film to be arranged, and a place close to the peripheral edge of the film for forming a protective film and opposite to each other. In this central (center of gravity) portion, five places including predetermined four places are arranged in almost point-symmetrical positions.

In the supporting sheet, the distance between the center (center of gravity) of the cutting position of the test piece is preferably 50~200mm. By setting in this way, the S value and L value of the adhesive layer can be obtained with higher precision.

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

The cross section of the test piece can be formed according to a known method. For example, by using a known cross-section sample preparation device (cross-section polishing machine), it is possible to form a cross-section in a test piece with suppressed variation and high reproducibility.

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

In the above cross-section of each test piece, measure the area of the minimum value and maximum value of the thickness of the adhesive layer, so that the thickness of each layer (substrate, adhesive layer, etc.) that constitutes the test piece is perpendicular to the lamination direction (approximately relative to each lamination layer). Or the parallel direction of the exposed surface) is preferably a region of 50-1500 μm. By setting according to this, the minimum value and maximum value of the thickness of the adhesive layer can be measured with high efficiency and high precision.

When comparing the minimum value of the thickness of the adhesive layer between the support sheet that has not yet constituted the composite sheet for protective film formation and the support sheet that has constituted the composite sheet for protective film formation, the minimum values are the same as each other, or the minimum value has been formed. The above-mentioned minimum value of the support sheet of the composite sheet for film formation is slightly smaller, and the difference is still negligible even when it is so small. The same applies to the maximum thickness of the adhesive layer. That is, when the maximum value of the thickness of the adhesive layer is compared between the support sheet that has not yet constituted the composite sheet for protective film formation and the support sheet that has constituted the composite sheet for protective film formation, the maximum values are the same as each other, or The above-mentioned maximum value of the support sheet constituting the composite sheet for forming a protective film is slightly small, and when it is so small, the difference is negligible. Therefore, the S value and L value of the adhesive layer can also be obtained by using the test piece cut out from the composite sheet for protective film formation instead of the support sheet in the same way as when using the test piece cut out from the support sheet. When using the test piece cut out from the composite sheet for protective film formation according to this, if the ratio of the L value of the adhesive layer to the S value of the adhesive layer (L value/S value) is 1.2 or more and less than 5.0, the protection The composite sheet for film formation reflects the above-mentioned effects of the present invention.

That is, a 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 of the support sheet; When the test pieces are cut from 5 places of the composite sheet, and then the minimum value and maximum value of the thickness of the adhesive layer are calculated for the 5 test pieces, the average value of the above maximum value (L value) is relative to the average value of the above minimum value (S value) ratio (L value/S value) is 1.2 or more and less than 5.0.

In addition, the test piece cut out from the composite sheet for protective film formation was obtained by cutting the composite sheet for protective film formation in the thickness direction, and included the small pieces which constituted all the layers of the composite sheet for protective film formation.

Hereinafter, the overall structure of the composite sheet for protective film formation of this invention is demonstrated, referring drawings. In addition, in the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, some important parts may be enlarged and shown for convenience, and the dimensional ratio of each component may not necessarily be the same as the actual size.

FIG. 1 is a schematic cross-sectional view of a support sheet and a composite sheet for forming a protective film according to an embodiment of the present invention. The composite sheet 1A for protective film formation shown here includes the base material 11, the adhesive agent layer 12 is provided on the base material 11, and the film 13 for protective film formation is provided on the adhesive agent 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, has a laminated protective layer on one side (also referred to as "the first surface" in this specification) 10a of the support sheet 10. Configuration of the thin film 13 for film formation. Moreover, 1 A of composite sheets for protective film formation are provided with the peeling film 15 on the film 13 for protective film formation further.

In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one side (also referred to as "the first side" in this specification) 11a of the base material 11, and an adhesive layer 12 is laminated on the side opposite to the side of the base material 11 ( Also referred to as "the first surface" in this specification) 12a, the protective film forming film 13 is laminated on the surface opposite to the side of the protective film forming film 13 facing the adhesive layer 12 (also referred to as "the first surface" in this specification). Surface ") 13a (i.e., the area near the peripheral edge), the adhesive layer 16 for the jig is laminated, and the first surface 13a of the film 13 for forming a protective film is not laminated with the adhesive layer 16 for the jig. The release film 15 is laminated with the adhesive layer 16 not in contact with one side 16a (upper surface and side surfaces) of the film 13 for forming a protective film. In addition, in FIG. 1, element code|symbol 13b has shown the surface (also called "2nd surface" in this specification) of the film 13 for protective film formation which faces the adhesive agent layer 12 side.

The jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or may have a multi-layer structure by laminating layers containing an adhesive component on both sides of a core sheet.

In 1 A of composite sheets for protective film formation, the 1st surface 11a of the base material 11 is an uneven|corrugated surface. In addition, the adhesive layer 12 is provided in the state which directly contacts the 1st surface (concave-convex surface) 11a of the base material 11. As shown in FIG. Therefore, the surface 12b of the adhesive layer 12 on the side facing the substrate 11 (also referred to as "the second surface" in this specification) is a concave-convex surface.

In the composite sheet 1A for forming a protective film, the surface 11b of the substrate 11 on the side opposite to the adhesive layer 12 (also referred to as "the second surface" in this specification) 11b may be a concave-convex surface or a smooth surface (non-concave-convex surface, bright surface). glossy surface), but smooth surface is preferred. The second surface 11b of the substrate 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 film 13 for forming a protective film. About "concave-convex surface" and "smooth surface", details will be given later.

The composite sheet 1A for forming the protective film shown in FIG. On the surface 16a of the adhesive layer 16, jigs such as a ring frame are attached to the upper surface and used.

Fig. 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 together. In addition, in FIG. 2 and subsequent figures, the same component elements shown in the already-described figures are given the same reference numerals as those in the previously-described figures, and detailed description thereof will be omitted.

The composite sheet 1B for protective film formation shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 1 except that the adhesive layer 16 for jigs 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 11a of the base material 11, and the film 13 for forming a protective film is laminated on the entire first surface 12a of the adhesive layer 12. The release film 15 is laminated on the entire first surface 13 a of the forming film 13 .

Also in the composite sheet 1B for protective film formation, the 1st surface 11a of the base material 11 belongs to an uneven|corrugated surface. Furthermore, the adhesive layer 12 is provided in a state of being in direct contact with the first surface (concave-convex surface) 11 a of the base material 11 . Therefore, the surface (second surface) 12b of the adhesive layer 12 on the side facing the substrate 11 is a concave-convex 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 an uneven surface or a smooth surface (non-uneven surface). A smooth surface is preferred.

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

Fig. 3 is a schematic cross-sectional view of a composite sheet for forming a protective film and a support sheet according to yet another embodiment of the present invention. The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1B for forming a protective film shown in FIG. 2 except that the shape of the film for forming a protective film is different. That is, 1 C of composite sheets for protective film formation include the base material 11, the adhesive agent layer 12 is included on the base material 11, and the film 23 for protective film formation is provided on the adhesive agent layer 12 further. 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 (the surface facing the protective film forming film 23 side) 10a of the support sheet 10, The film 23 for forming a protective film is laminated. Moreover, 1 C of composite sheets for protective film formation further include the peeling film 15 on the film 23 for protective film formation.

In the protective film forming composite sheet 1C, the adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film forming layer is laminated on a part (that is, the central region) of the first surface 12a of the adhesive layer 12. film23. In addition, on the first surface 12a of the adhesive layer 12, the area where the protective film forming film 23 is not laminated and the surface 23a (the upper surface and the side surface) of the protective film forming film 23 that is not in contact with the adhesive layer 12 are laminated. Peel off the film 15. In addition, in FIG. 3, element code|symbol 23b has shown the surface (also called "2nd surface" in this specification) of the film 23 for protective film formation which faces the adhesive agent layer 12 side.

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

Also in 1 C of composite sheets for protective film formation, the 1st surface 11a of the base material 11 is an uneven|corrugated surface. Furthermore, the adhesive layer 12 is designed to be in a state of directly contacting the first surface (concave-convex surface) 11 a of the substrate 11 . Therefore, the surface (second surface) 12b of the adhesive layer 12 on the side facing the substrate 11 is a concave-convex surface. In the composite sheet 1C for forming a protective film, the second surface 11b of the substrate 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-concave-convex surface), But the smooth side is better.

The composite sheet 1C for protective film formation shown in FIG. In the first surface 12a of the first surface 12a, the area where the film 23 for forming a protective film is not laminated is used by affixing a jig such as a ring frame.

In addition, in the composite sheet 1C for forming a protective film shown in FIG. 3 , an adhesive for a jig as shown in FIG. layers (not shown). Such a composite sheet 1C for forming a protective film including an adhesive layer for a jig is used by affixing a jig such as a ring frame on the adhesive layer for a jig, similarly to the composite sheet for forming a protective film shown in FIG. 1 .

Accordingly, the composite sheet for protective film formation may include the adhesive layer for jigs regardless of the form of the support sheet and the thin film for protective film formation. However, generally, as shown in FIG. 1 , in the protective film-forming composite sheet including the jig adhesive layer, it is preferable to provide the jig adhesive layer on the protective film-forming film.

The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to those shown in FIGS. 1 to 3 , and part of them shown in FIGS. 1 to 3 may be changed or deleted within the scope not to impair the effects of the present invention. configuration, and 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 protective film formation of this invention, a support sheet may be laminated|stacked and comprised in the thickness direction in order of a base material, an intermediate|middle layer, and an adhesive agent layer. The intermediate layer system can be selected arbitrarily according to the purpose. In addition, the composite sheet for protective film formation shown in FIGS. 1-3 may provide layers other than the said intermediate layer in arbitrary places. In addition, in the composite sheet for protective film formation, gaps may be partially generated between the release film and the layers directly in contact with the release film. In addition, the size, shape, etc. of each layer of the composite sheet for protective film formation can be adjusted arbitrarily 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 is in direct contact with the concave-convex surface (first surface) of the base material, in other words, between the base material and the adhesive layer. An intermediate layer is not provided, but an adhesive layer is laminated in direct contact with the substrate. Furthermore, in the composite sheet for forming a protective film, it is preferable that the film for forming a protective film is directly in contact with 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 film for forming a protective film is laminated in direct contact with the adhesive layer. Furthermore, it is more preferable that the composite sheet for forming a protective film satisfies all of these conditions, that is, the substrate, the adhesive layer, and the thin film for forming a protective film are in direct contact with each other and laminated in the thickness direction in the order of the substrate.

The above-mentioned supporting sheet is preferably transparent. The supporting sheet may also be colored or vapor-deposited with other layers according to the purpose. For example, when the thin film for forming a protective film is energy ray curable, it is preferable that the support sheet allows the energy ray to penetrate.

In this specification, the so-called "energy rays" refer to energy quanta in electromagnetic waves or charged particle beams, such as ultraviolet rays, radiation rays, electron beams, etc. The ultraviolet rays 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 as an ultraviolet source. Electron beams can be irradiated with those generated by an electron beam accelerator or the like. In this specification, "energy ray curability" refers to the property of being cured by irradiation of energy ray, and "non-energy ray curability" refers to the property of not curing even when irradiated with energy ray.

The wavelength 375nm light transmittance of the supporting sheet is preferably above 30%, more preferably above 50%, and especially excellent above 70%. When the above-mentioned light transmittance is in such a range, when energy rays (ultraviolet rays) are irradiated to the film for forming a protective film through the support sheet, the degree of hardening of the film for forming a protective film is further increased. The upper limit of the transmittance of light with a wavelength of 375 nm of the support sheet is not particularly limited. For example, the above-mentioned light transmittance is preferably below 95%.

The wavelength 532nm light transmittance of the support sheet is preferably above 30%, more preferably above 50%, and most preferably above 70%. When the above-mentioned light transmittance is in such a range, marking can be performed more clearly when irradiating laser light to the thin film for protective film formation or a protective film via a support sheet and marking on it. The upper limit of the transmittance of light with a wavelength of 532 nm of the support sheet is not particularly limited. For example, the light transmittance mentioned above is preferably below 95%.

The wavelength 1064nm light transmittance of the supporting sheet is preferably above 30%, more preferably above 50%, and especially excellent above 70%. When the above-mentioned light transmittance is in such a range, marking can be performed more clearly when irradiating laser light to the thin film for protective film formation or a protective film via a support sheet and marking on it. The upper limit of the transmittance of light with a wavelength of 1064 nm of the support sheet is not particularly limited. For example, the above-mentioned light transmittance is preferably below 95%.

The penetration clarity of the support sheet is preferably above 30, more preferably above 100, and especially excellent above 200. When the above-mentioned penetration clarity is within such a range, it is possible to more easily confirm the floating and falling off of the film for forming a protective film, marking defects, and chipping through the support sheet. The penetration clarity of the support sheet is not particularly limited. For example, the above-mentioned penetration clarity can be below 430. The penetration clarity of the support sheet can be measured in accordance with JIS K 7374-2007.

Next, each layer which comprises a support sheet and the composite sheet for protective film formation is demonstrated in detail.

○Substrate The aforementioned substrate is in the form of a sheet or a film, and has a concave-convex surface.

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

The base material may have a concave-convex surface only on one side, or both sides may have a concave-convex surface, preferably only one side has a concave-convex surface. In other words, among the above-mentioned substrates, only one side thereof is preferably smooth. In the support sheet, the concave-convex surface of the base material becomes the surface on which the adhesive layer is provided.

The substrate may be composed of only one layer (single layer), or may be composed of multiple layers of two or more layers. When composed of multiple layers, these multiple layers may be the same or different from each other. The combination is not particularly limited. When the base material is composed of multiple layers, among these multiple layers, one of the outermost surfaces (the surface closest to the adhesive layer, or both sides of the surface closest to the adhesive layer and the surface farthest from the adhesive layer) becomes the above-mentioned concavities and convexities. noodle.

This description is not limited to the case of the base material. The so-called "a plurality of layers may be the same or different from each other" means "all the layers may be the same, or all the layers may be different, or only some of the layers may be the same." ; Also, the so-called "a plurality of layers are different from each other" means "at least one of the constituent materials and thicknesses of each layer is different from each other."

The maximum height roughness (Rz) measured in accordance with JIS B 0601:2013 on the concave-convex surface (first surface) on the side where the adhesive layer is provided on the base material is preferably 0.01~10μm, more preferably 0.1~9μm , The best is 0.5~8.5μm. When the said Rz of a base material is more than the said lower limit value, it suppresses that troubles arise when winding up a base material independently into a roll shape, and unwinding. Moreover, in the manufacturing process of the support sheet or the composite sheet for protective film formation, it suppresses that troubles at the time of winding up and unwinding are similarly suppressed about the laminate containing a base material. On the other hand, when the above-mentioned Rz of the base material is not more than the above-mentioned upper limit, the laminarity 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 improved. Sex is better. In addition, the term "lamination property" in this specification refers to the normality of the lamination state of the target two layers unless otherwise stated. "Good laminarity" means, for example, that there is no unbonded area (void) between two adjacent layers, or that the number of unbonded areas is small and the interlayer distance between unbonded areas is small.

When both surfaces of the substrate are concave-convex, the concave-convex degrees of the two surfaces may be the same or different from each other.

Various resins can be mentioned as a constituent material of the above-mentioned base material, for example. The above-mentioned resin system can be exemplified: polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, polyformaldehyde Polyolefins other than polyethylene such as pentene and norbornene resins; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-norcamphene Ethylene-based 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-naphthalate Esters, polyesters such as wholly aromatic polyesters with aromatic ring groups in all their constituent units; copolymers of two or more of the above-mentioned polyesters; poly(meth)acrylates; polyurethanes; polyurethane acrylates; polyimides ; Polyamide; Polycarbonate; Fluorine resin; Polyacetal; Furthermore, the above-mentioned resin can also be, for example, a polymer alloy such as a mixture of the above-mentioned polyester and other resins. For the above-mentioned polymer blend of polyester and other resins, preferably, the amount of resins other than polyester is relatively small. Furthermore, the above-mentioned resin may also be, for example: a cross-linked resin obtained by cross-linking one or two or more of the above-mentioned resins exemplified so far; Modified resins such as ionic polymers.

In this specification, "(meth)acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same is true for similar terms about (meth)acrylic acid. For example, the so-called "(meth)acryl" includes the concepts of both "acryl" and "methacryl"; the so-called "(meth)acryl" "Ester" is a concept that includes both "acrylate" and "methacrylate".

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

The thickness of the substrate is preferably within the range of 50-300 μm, more preferably within the range of 60-150 μm. When the thickness of a base material exists in such a range, the flexibility of the said composite sheet for protective film formation, and the adhesiveness to a semiconductor wafer or a semiconductor wafer can be improved more. As mentioned above, since the substrate has a concave-convex surface, its thickness varies depending on the location of the substrate. Therefore, the minimum value of the thickness of the base material can be more than the above-mentioned lower limit value, and the maximum value of the base material thickness can be below the above-mentioned upper limit value. In addition, the "substrate thickness" refers to the thickness of the entire substrate, for example, the thickness of a substrate composed of a plurality of layers refers to the total thickness of all layers constituting the substrate.

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

For example, according to the method described above, a test piece is cut from a plurality of places (for example, 5 places) of the composite sheet for forming a support sheet or a protective film, and the minimum value and the maximum value of the thickness of the base material are obtained for the test piece, and then obtained from these When the values are further calculated for these minimum and maximum values, the above-mentioned minimum value average can be above the lower limit of the above-mentioned base material thickness, and the above-mentioned maximum value average can also be below the above-mentioned upper limit of the above-mentioned base material thickness. .

In addition to the main constituent materials such as the above-mentioned resin, the base material may also contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

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

In order to improve the adhesiveness of the substrate in direct contact with the adhesive layer placed on it, the surface can also be subjected to corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone and ultraviolet irradiation treatment. , Flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments, etc. Furthermore, the surface of the substrate can also be treated with a primer. Furthermore, the base material may have: an antistatic coating layer; and a layer that prevents the base material from sticking to other sheets, the base material from sticking to an adsorption platform, etc. when the composite sheet for forming a protective film is stacked and stored.

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

When using a base material that does not have a rough surface (in other words, a base material whose both sides are smooth), it is only necessary to perform a roughening treatment on the smooth surface of the base material. The roughening treatment can be performed according to a known method. For example, by using a metal roll or a metal plate having a concave-convex surface and pressing the above-mentioned concave-convex surface against the smooth surface of the substrate, the smooth surface of the substrate can be subjected to the concave-convex treatment. At this time, it is preferable to press the heated metal roll or metal plate against the smooth surface of the base material. In addition, the smooth surface of the base material may be roughened by sandblasting, solvent treatment, or the like.

○Adhesive layer The above-mentioned adhesive layer is in the form of a sheet or a film. In the adhesive layer, whether there is an intermediate layer between the substrate and the adhesive layer or not, it will be affected by the above-mentioned uneven surface of the substrate, so that at least the surface facing the substrate will become an uneven surface.

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

Here, referring to the drawings, the base material and the adhesive layer will be described in more detail. Fig. 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 protective film formation shown in FIG. 1 is taken as an example and demonstrated. In addition, illustration of the release film is omitted in FIG. 4 .

As described above, the first surface 11a of the substrate 11 is a concave-convex surface. However, the adhesive layer 12 is provided in direct contact with the first surface (concave-convex surface) 11 a 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 is also a concave-convex surface.

The thickness T _a of the adhesive layer 12 is not constant, and varies according to the location of the adhesive layer 12 . Here, the minimum thickness of the adhesive layer 12 is represented by symbol T _a1 , and the maximum thickness of the adhesive layer 12 is represented by symbol T _a2 .

In the protective film forming composite sheet 1A, test pieces are cut out from 5 places, and cross sections are formed on these 5 test pieces, and the minimum value T _a1 and maximum value T _a2 of the thickness of the adhesive layer are respectively obtained for the newly formed cross sections. . Then, the average value (the above-mentioned S value) is obtained from at least five T _a1 values, and the average value (the above-mentioned L value) is obtained from at least five T _a2 values, and the ratio of the above-mentioned L value to the above-mentioned S value is calculated. The ratio (L value/S value) was 1.2 or more and less than 5.0.

Cut the test piece from the composite sheet 1A for protective film formation, form the cross-section of the test piece, and measure the minimum value T _a1 and maximum value T _a2 of the thickness of the adhesive layer in the above-mentioned cross-section. The same was done in the case of cutting out the test piece from the support sheet for forming the composite sheet.

In addition, the enlarged cross-sectional view of the support sheet which 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 protective film formation, it is shown here that between the base material 11 and the adhesive layer 12 , there is an unbonded region (also referred to as "unbonded region" in this specification) 91 . However, even if the composite sheet 1A for forming a protective film has such an unbonded region 91 , the composite sheet 1A for forming a protective film whose size of the non-bonded region 91 in the thickness direction of the composite sheet 1A for forming a protective film is, for example, 0.5 μm or less, The lamination property between the base material 11 and the adhesive layer 12 is still good, which can be said to have good characteristics.

In addition, in this specification, "the size of the unbonded area in the thickness direction of the composite sheet for protective film formation" means "the distance between two adjacent layers in the thickness direction of the sheet for protective film formation in the composite sheet for protective film formation." , sometimes simply referred to as "interlayer distance". For example, the "size of the unbonded region 91 in the thickness direction of the protective film forming composite sheet 1A" refers to "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 unbonded area (distance between layers) varies in one place, the maximum value is adopted as the size of the unbonded area (distance between layers).

The size (distance between layers) of the unbonded area can be measured by the same method as, for example, the thickness of the above-mentioned adhesive layer. That is, in the same way as when calculating the thickness of the adhesive layer, a cross section is formed in the test piece of the composite sheet for forming a protective film, and then the size of the unbonded area can be obtained from this cross section. Alternatively, without producing a test piece, a cross-section can be formed on the protective film forming composite sheet itself, and then the size of the unbonded area can be obtained from this cross-section.

The size of the unbonded region 91 (the 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.

The composite sheet 1A for protective film formation may not exist the non-bonding area|region 91 at all.

Here, the composite sheet for forming a protective film 1A is taken as an example, and the base material and the adhesive layer are described. However, the composite sheet for forming a protective film 1B, the composite sheet for forming a protective film 1C, and other embodiments of the composite sheet for forming a protective film are described. In the case of the composite sheet, the base material and the adhesive layer are also the same.

The ratio of the L value of the adhesive layer to the S value of the adhesive layer (L value/S value) is not particularly limited on the premise that it is 1.2 or more and less than 5.0. The above-mentioned L value/S value is preferably 1.3 or more, more preferably 1.4 or more, for example, may be any one of 1.8 or more, 2.3 or more, and 2.7 or more. When the above-mentioned L value/S value exceeds the above-mentioned lower limit value, the adhesive layer can fully follow the unevenness of the base material, no peeling will occur between the base material layer and the adhesive layer, and the tight adhesion between the base material layer and the adhesive layer Sex is better.

The above-mentioned L value/S value is preferably at most 4.3, more preferably at most 3.7, most preferably at most 3.1, for example, may be at most 2.8. When the said L value/S value is below the said upper limit, the marking visibility of a protective film or a film for protective film formation via a support sheet becomes more favorable.

The above-mentioned L value/S value can be appropriately adjusted within the range set by any combination of the above-mentioned preferred lower limit and upper limit. For example, the above-mentioned L value/S value is preferably 1.2~4.3, more preferably 1.3~3.7, and particularly good is 1.4~3.1. However, these are only examples of the above-mentioned L value/S value.

The S value of the adhesive layer is not particularly limited on the premise that the ratio of the L value to the S value (L value/S value) is 1.2 or more and less than 5.0 when setting the L value of the adhesive layer. The best is 1.5 μm or more, more preferably 1.7 μm or more, and the most preferred is 1.9 μm or more, for example, it may be any of 3 μm or more, 4.5 μm or more, and 6 μm or more. When the above-mentioned S value is 1.5 μm or more, the laminarity between the adhesive layer and the film for forming a protective film can be easily improved.

On the other hand, the S value of the adhesive layer may be, for example, 9 μm or less. Such an adhesive layer can be formed more easily.

The S value of the adhesive layer can be properly adjusted within the range set by any combination of the above preferred lower limit and upper limit. For example, the S value of the adhesive layer is preferably 1.5-9 μm, more preferably 1.7-9 μm, and most preferably 1.9-9 μm, for example, any one of 3-9 μm, 4.5-9 μm, and 6-9 μm. However, these are only examples of the S value of the adhesive layer.

The L value of the adhesive layer is not particularly limited as long as the ratio (L value/S value) to the above S value is 1.2 or more and less than 5.0, but it is preferably 15 μm or less, more preferably 14.5 μm Below, for example, any one of 13 μm or less, 11 μm or less, 9 μm or less, and 7 μm or less may be used. When the said L value is below the said upper limit, the marking visibility of a protective film or a film for protective film formation via a support sheet becomes more favorable.

On the other hand, the L value of the adhesive layer may be, for example, 1.5 μm or more. Such an adhesive layer can be formed more easily.

The L value of the adhesive layer can be properly adjusted within the range set by any combination of the above preferred lower limit and upper limit. For example, the L value of the adhesive layer is preferably 1.5-15 μm, more preferably 1.5-14.5 μm, for example, any one of 1.5-13 μm, 1.5-11 μm, 1.5-9 μm, and 1.5-7.

The combination of the S value and the L value of the adhesive layer can be set arbitrarily so that the ratio of the L value to the S value (L value/S value) satisfies the above upper limit and lower limit. For example: combination of S value 1.5~9μm and L value 1.5~15μm; combination of S value 1.5~9μm and L value 1.5~14.5μm; combination of S value 1.7~9μm and L value 1.5~15μm; S value 1.7~9μm , combination of L value 1.5~14.5μm; combination of S value 1.9~9μm, L value 1.5~15μm; combination of S value 1.9~9μm, L value 1.5~14.5μm; S value 3~9μm, L value 1.5~15μm The combination of is equal to any one.

The thickness of the adhesive layer (for example, T _a ) is not particularly limited as long as the ratio of the above-mentioned L value to the S value is satisfied. For example, the thickness of the adhesive layer may also be 1.5-15 μm.

In addition, the "thickness of the adhesive layer" refers to the thickness of the entire adhesive layer, for example, the thickness of an adhesive layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive layer. From this point of view, the minimum and maximum thicknesses of the above-mentioned adhesive layer are specified.

The adhesive layer system contains an adhesive. Examples of the above adhesive system include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. Acrylic resin is preferred.

In this specification, the term "adhesive resin" is a concept that includes both adhesive resin and adhesive resin. For example, not only the resin itself has adhesiveness, but also the resin exhibits adhesiveness by using other components such as additives in combination. Resins, resins that exhibit adhesiveness due to the presence of triggers such as heat or water, etc.

The adhesive layer is preferably transparent. The adhesive layer can also be colored according to the purpose. For example, when the film for forming a protective film is energy ray curable, it is preferable for the adhesive layer to pass through the energy ray.

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

＜＜Adhesive composition＞＞ The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition can be applied on the surface to be formed with the adhesive layer and dried as necessary to form the adhesive layer at the target site. A more specific method for forming the adhesive layer will be described in detail later together with methods for forming the outer layers. The content ratio of the components that do not vaporize at normal temperature in the adhesive composition is usually the same as the content ratio of the above-mentioned components in the adhesive layer.

In this specification, "normal temperature" refers to a temperature that is not particularly cold or hot, that is, a normal 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 coater (Air-knife-coater), a blade coater (Blade-coater), a rod 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. The method of cloth machine.

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

When the adhesive layer is energy ray-curable, the adhesive composition containing the energy ray-curable adhesive (that is, the energy ray-curable adhesive composition) includes, for example, a 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; containing a non-energy ray-curable adhesive resin ( The side chain of I-1a), the adhesive composition (I-2) of the energy ray-curable adhesive resin (I-2a) (hereinafter referred to as "adhesive resin (I-2a)") with unsaturated groups introduced; Adhesive composition (I-3) containing the above-mentioned adhesive resin (I-2a), an energy ray-curable compound, and the like.

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

[Adhesive resin (I-1a)] The above-mentioned adhesive resin (I-1a) is preferably an acrylic resin. The above-mentioned acrylic resin is, for example, an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate. The structural unit system which the said acrylic resin has may be only 1 type, and may be 2 or more types, and when there are 2 or more types, the combination and ratio can be chosen arbitrarily.

The above-mentioned alkyl (meth)acrylate can be, for example, the carbon number of the alkyl constituting the alkyl ester is 1-20, and the above-mentioned alkyl is preferably linear or branched. Alkyl (meth)acrylate can be more systematic, for example: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl methacrylate, 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, Myristyl (meth)acrylate (myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Cetyl (meth)acrylate (palmityl (meth)acrylate), Heptadecyl (meth)acrylate, Octadecyl (meth)acrylate Base ester (stearyl (meth)acrylate), nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc.

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

The above-mentioned acrylic polymer preferably has a constituent unit derived from a functional group-containing monomer in addition to a constituent unit derived from an alkyl (meth)acrylate. The above-mentioned functional group-containing monomer can be exemplified by reacting the above-mentioned functional group with the cross-linking agent described later to become a cross-linking origin, by reacting the above-mentioned functional group with the unsaturated group in the unsaturated group-containing compound described later, etc. One that introduces an unsaturated group into the side chain of an acrylic polymer.

The above-mentioned functional groups in the functional group-containing monomers include, for example, hydroxyl groups, carboxyl groups, amino groups, epoxy groups, and the like. That is, the functional group-containing monomer system includes, for example, a hydroxyl-containing monomer, a carboxyl-containing monomer, an amino-containing monomer, an epoxy-containing monomer, and the like.

The above-mentioned hydroxyl-containing monomer system can be exemplified: (meth) hydroxymethyl acrylate, (meth) acrylate-2-hydroxyethyl, (meth) acrylate-2-hydroxypropyl, (meth) acrylate-3 -Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates ; Non-(meth)acrylic unsaturated alcohols (unsaturated alcohols without a (meth)acryl skeleton) such as vinyl alcohol and allyl alcohol.

The above-mentioned carboxyl group-containing monomer system can be exemplified for example: (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids with ethylenically unsaturated bonds); fumaric acid, itaconic acid, cis Butenedioic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the above-mentioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. Carboxyalkyl (meth)acrylate and the like.

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

The functional group-containing monomer system constituting the above-mentioned acrylic polymer may be only one type, or may be two or more types. If there are two or more types, the combination and ratio can be selected arbitrarily.

In the above-mentioned acrylic polymer, the content of the structural units derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and most preferably 3 ~27% by mass.

In addition to the constituent units derived from alkyl (meth)acrylate and functional group-containing monomers, the above-mentioned acrylic polymer system may further have constituent units derived from other monomers. The other monomers mentioned above are not particularly limited on the premise that they can be copolymerized with alkyl (meth)acrylate or the like. Examples of other monomer systems mentioned above include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

The above-mentioned other monomers constituting the above-mentioned acrylic polymer may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof can be selected arbitrarily.

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

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

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 most preferably 15 to 90% by mass.

[Energy Beam Curing Compound] The aforementioned energy ray-curable compound contained in the adhesive composition (I-1) is, for example, a monomer or oligomer having an energy ray polymerizable unsaturated group and curable by energy ray irradiation. Among the energy ray-curing compounds, monomer systems include, for example, trimethylolpropane tris[(meth)acrylate], neopentylthritol (meth)acrylate, neopentylthritol tetra[(meth)acrylate] Acrylate], Dineopentyl Glycol Hexa[(meth)acrylate], 1,4-Butanediol Di[(meth)acrylate], 1,6-Hexanediol (meth)acrylate, etc. Multi-component (meth)acrylate; urethane (meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray-curable compounds, the oligomers include oligomers obtained by polymerizing the monomers listed above, and the like. The energy ray-curable compound is preferably urethane (meth)acrylate or urethane (meth)acrylate from the viewpoint of having a large molecular weight and not easily lowering the storage elastic modulus of the adhesive layer. oligomers.

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

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 most preferably 10 to 85% by mass.

[Crosslinking agent] When the adhesive resin (I-1a) is derived from a structural unit derived from an alkyl (meth)acrylate, when the above-mentioned acrylic polymer having a 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 said crosslinking agent is what reacts with the said functional group, and crosslinks adhesive resin (I-1a) mutually, for example. The cross-linking agent system can be, for example, isocyanate-based cross-linking agents (with isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates. cross-linking agent); epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (cross-linking agent with glycidyl group); hexa[1-(2-methyl)-aziridinyl] triphosphate triphosphate Aziridine-based cross-linking agents such as oxazine (cross-linking agent with aziridine group); metal chelating cross-linking agent such as aluminum chelate (cross-linking agent with metal chelating structure); isocyanurate It is a crosslinking agent (crosslinking agent with isocyanuric acid skeleton), etc. From the viewpoints of improving the cohesion of the adhesive to enhance the adhesion of the adhesive layer, as well as being easy to obtain, the cross-linking agent is preferably an isocyanate-based cross-linking agent.

The cross-linking agent 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 thereof can be selected arbitrarily.

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

[Photopolymerization Initiator] The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator fully advances hardening reaction even if it irradiates energy rays of low energy, such as an ultraviolet-ray.

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。The above-mentioned photopolymerization initiators can be exemplified as: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoin Benzoin compounds such as methyl ester, benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy- Acetophenone compounds such as 1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzene Acylated phosphine oxide compounds such as formyl diphenylphosphine oxide; thioether compounds such as benzyl phenyl sulfide and tetramethylammonium thioformyl monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenone; azo Azo compounds such as bisisobutyronitrile; titanocene compounds such as titanocene; oxygen sulfur 𠮿

isosulfur

Compounds; peroxy compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; diphenyl ketone; 2,4-diethyloxysulfurium

; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone, etc. In addition, the said photoinitiator can also use, for example: a quinone compound, such as 1-chloroanthraquinone; Photosensitizers, such as an amine, etc. can also be used.

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

The content of the photopolymerization initiator in the adhesive composition (I-1) 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. 0.05 to 5 parts by mass, and 0.05 to 5 parts by mass.

[Other additives] The adhesive composition (I-1) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effect of the present invention. The above-mentioned other additives can be for example: antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, reaction inhibitors, etc. Known additives such as retarder, crosslinking accelerator (catalyst). In addition, the so-called "reaction retarder" is to suppress, for example, the unintended cross-linking of the adhesive composition (I-1) during storage due to the catalytic action mixed in the adhesive composition (I-1). reaction. Examples of the reaction retarder include those that form a chelate complex with a chelate catalyst, and more specifically, those that have two or more carbonyl groups (—C(=O)—) in one molecule.

The other additives 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 thereof can be selected arbitrarily.

The content of other additives in the adhesive composition (I-1) is not particularly limited, as long as they are properly selected according to the type.

[solvent] The adhesive composition (I-1) may also contain a solvent. The adhesive composition (I-1) improves the applicability to the coating target surface by containing a solvent.

The above-mentioned solvent is preferably an organic solvent, and the above-mentioned organic solvent can be for example: ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; fatty acids such as cyclohexane and n-hexane. Aromatic hydrocarbons; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol, etc.

For example, the above-mentioned solvent can be directly used in the adhesive composition (I-1) when the adhesive resin (I-1a) is produced without being removed from the adhesive resin (I-1a), or it can be used in the adhesive When the agent composition (I-1) is produced, the same or a different type of solvent as that used for the production of the adhesive resin (I-1a) is additionally 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 thereof can be selected arbitrarily.

The solvent content in the adhesive composition (I-1) is not particularly limited, and may be appropriately adjusted.

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

[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 not only the above-mentioned energy ray polymerizable unsaturated group, but also has the function of reacting with the functional group in the adhesive resin (I-1a) to react with the adhesive resin (I-1a). Bonded base compounds. The aforementioned energy ray polymerizable unsaturated group can be, for example, (meth)acryl, vinyl (ethenyl group), allyl (2-propenyl), etc., preferably (meth)acryl. The group capable of bonding to the functional group in the adhesive resin (I-1a) includes, for example, an isocyanate group and a glycidyl group capable of bonding to a hydroxyl group or an amine group, and a group capable of bonding to a carboxyl group or an epoxy group. The hydroxyl group and amino group of the junction.

Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryl isocyanate, glycidyl (meth)acrylate, and the like.

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

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

[Crosslinking agent] When the adhesive resin (I-2a) is, for example, the same 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) includes the same ones as those in the adhesive composition (I-1). The cross-linking agent contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof can be selected arbitrarily.

The content of the crosslinking agent in the above adhesive composition (I-2) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). 0.3 to 15 parts by mass of Tejia.

[Photopolymerization Initiator] The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator fully advances hardening reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.

The photopolymerization initiator in the adhesive composition (I-2) includes the same ones as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof can be selected arbitrarily.

The content of the photopolymerization initiator in the adhesive composition (I-2) 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 content of the adhesive resin (I-2a). Parts by mass, especially 0.05-5 parts by mass.

[Other additives] The adhesive composition (I-2) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effects of the present invention. The above-mentioned other additives in the adhesive composition (I-2) include the same ones as the other additives in the adhesive composition (I-1). The other additives 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 thereof can be selected arbitrarily.

The content of other additives in the adhesive composition (I-2) is not particularly limited, as long as they are properly selected according to the type.

[solvent] The adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). Examples of the solvent in the adhesive composition (I-2) include the same solvents as those 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 thereof can be selected arbitrarily. The solvent content in the adhesive composition (I-2) is not particularly limited, and may be appropriately adjusted.

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

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

[Energy Beam Curing Compound] The above-mentioned energy ray-curable compound contained in the adhesive composition (I-3) includes monomers and oligomers that have an energy-ray-polymerizable unsaturated group and can be cured by irradiation with energy rays. Composition (I-1) contains the same energy ray curable compound. The above-mentioned energy ray-curable compound contained in the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof can be selected arbitrarily.

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

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

The photopolymerization initiator in the adhesive composition (I-3) includes the same ones as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof can be selected arbitrarily.

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 energy ray-curable compound. Parts by mass, more preferably 0.03-10 parts by mass, and especially preferred 0.05-5 parts by mass.

[Other additives] The adhesive composition (I-3) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the above-mentioned other additives include the same ones as those in the adhesive composition (I-1). The other additives 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 thereof can be selected arbitrarily.

The content of other additives in the adhesive composition (I-3) is not particularly limited, as long as they are properly selected according to the type.

[solvent] The adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). Examples of the solvent in the adhesive composition (I-3) include the same solvents as those in 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 thereof can be selected arbitrarily. The solvent content in the adhesive composition (I-3) is not particularly limited, and may be appropriately adjusted.

<Adhesive compositions other than adhesive compositions (I-1) to (I-3)> Up to now, the descriptions have mainly focused on the adhesive composition (I-1), adhesive composition (I-2), and adhesive composition (I-3), but the components contained in these compositions that have been described can still be used in the same way. All adhesive compositions other than these three adhesive compositions (also referred to as "adhesive compositions other than adhesive compositions (I-1) to (I-3)" in this specification) are used.

Adhesive compositions other than the adhesive compositions (I-1) to (I-3) include energy ray-curable adhesive compositions, and non-energy ray-curable adhesive compositions. The composition of the non-energy ray-curable adhesive can include, for example, acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester The adhesive composition (I-4) that is a non-energy ray-curable adhesive resin (I-1a) such as resin preferably contains an acrylic resin.

Adhesive compositions other than adhesive compositions (I-1) to (I-3) preferably contain one or more crosslinking agents, and the content can be set to the same amount as the above-mentioned adhesive composition The same applies to (I-1) and the like.

＜Adhesive composition (I-4)＞ Adhesive composition (I-4) preferably includes one 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) includes the same ones as the adhesive resin (I-1a) in the adhesive composition (I-1). The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof can be selected arbitrarily.

The content of the adhesive resin (I-1a) in the adhesive composition (I-4) is preferably 5 to 99% by mass, more preferably 10%, relative to the total mass of the adhesive composition (I-4). ~95% by mass, 15% to 90% by mass for extra-fine products.

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 (that is, the content of the adhesive resin (I-1a) in the adhesive layer) , preferably 30-90% by mass, more preferably 40-85% by mass, and most preferably 50-80% by mass.

[Crosslinking agent] When the adhesive resin (I-1a) is derived from a structural unit derived from an alkyl (meth)acrylate, when the above-mentioned acrylic polymer having a 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.

Examples of the crosslinking agent in the adhesive composition (I-4) are the same as those in the adhesive composition (I-1). The cross-linking agent 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 thereof can be selected arbitrarily.

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

[Other additives] The adhesive composition (I-4) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the above-mentioned other additives include the same ones as those in the adhesive composition (I-1). The other additives 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 thereof can be selected arbitrarily.

The content of other additives in the adhesive composition (I-4) is not particularly limited, as long as they are properly selected according to the type.

[solvent] The adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). Examples of the solvent in the adhesive composition (I-4) include the same solvents as those in the adhesive composition (I-1). The solvent 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 thereof can be selected arbitrarily. The solvent content in the adhesive composition (I-4) is not particularly limited, and may be appropriately adjusted.

In the above 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 energy ray irradiation, the adhesive layer may not be cured at the same time. If the adhesive layer is cured simultaneously with the film for forming a protective film, the film for forming a protective film (that is, the protective film) after hardening and the adhesive layer will be adhered to such an extent that they cannot be peeled off at the interface. In this case, it is more difficult to peel off the semiconductor wafer (semiconductor wafer with protective film) with a hardened protective film forming film (i.e. protective film) on the back from the support sheet including the hardened adhesive layer, resulting in a protective film. The semiconductor chip cannot be picked up normally. In the above-mentioned supporting sheet, setting the adhesive layer as non-energy ray curable can surely avoid such disadvantages, so that the semiconductor wafer with the protective film can be picked up more easily.

Here, the effect of the non-energy ray curable adhesive layer is described, but even if the layer other than the adhesive layer is in direct contact with the protective film forming film of the support sheet, as long as the layer is non-energy ray curable , still achieve the same effect.

＜＜Manufacturing method of adhesive composition＞＞ Adhesive compositions other than adhesive compositions (I-1)~(I-3), such as adhesive compositions (I-1)~(I-3), adhesive compositions (I-4), are It can be obtained by blending the above-mentioned adhesive and, if necessary, components other than the above-mentioned adhesive, and other components constituting the adhesive composition. The order of addition of the respective components is not particularly limited, and two or more components may be added simultaneously. When using a solvent, the solvent can be mixed with any blending ingredient other than the solvent, and then the blended ingredient can be used after pre-diluted, or it can be used without pre-diluting any blended ingredient other than the solvent. A solvent is used in admixture with these blending components. When blending, the method of mixing the components is not particularly limited, for example: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing by using a mixer; a method of mixing by applying ultrasonic waves, etc. Properly selected from known methods. The addition of each component, and the temperature and time of mixing are on the premise that each blending component will not deteriorate, and there is no special limitation, as long as it is properly adjusted, the temperature is preferably 15~30°C.

◎Films for protective film formation The above thin film for forming a protective film forms a protective film by being cured, or by being uncured and maintaining the original state. This protective film is used to protect the semiconductor wafer or the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface). The protective film forming film is soft and can be easily attached to the object to be attached.

The above-mentioned thin film for protective film formation may be curable or non-curable. The thin film for forming a curable protective film may be either thermosetting or energy ray curable, or may have both thermosetting and energy ray curable properties. The thin film for protective film formation can be formed using the composition for protective film formation containing the constituent material.

In this specification, "non-curable" refers to the property that it will not be cured regardless of any means such as heating or energy ray irradiation. In the present invention, even after curing the film for forming a protective film, the laminate structure of the cured product of the support sheet and the film for forming the protective film (in other words, the support sheet and the protective film) can be maintained, this laminate is referred to as "Composite sheet for protective film formation".

The thin film for protective film formation may consist of 1 layer (single layer), or may consist of plural layers of 2 or more layers, regardless of its kind. When the thin film for protective film formation consists of plural layers, these plural layers may mutually be the same, and may be different.

Here, referring to FIG. 4 again, the adhesive layer and the film for forming a protective film will be further described in detail. As described above, the first surface 11a of the substrate 11 is a concave-convex surface. However, if the S value of the adhesive layer 12 is, for example, 1.5 μm or more, the influence of the uneven surface is suppressed, and the degree of unevenness of the first surface 12 a of the adhesive layer 12 is reduced. Therefore, the laminarity between the adhesive layer 12 and the film 13 for protective film formation becomes favorable. For example, even if there are these unbonded regions (non-bonded regions) 92 between the adhesive layer 12 and the film 13 for forming a protective film, the number of them spans the protective film in the composite sheet 1A for forming a protective film. In the total area where the formation thin film 13 is formed, there are still very few places such as three or less. The non-bonded region 92 can be easily confirmed by observing the composite sheet 1A for protective film formation, for example from the base material 11 side.

Furthermore, even if the composite sheet 1A for protective film formation has such an unbonded region 92, the size (distance between layers) of the non-bonded 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 film formation, the laminarity between the adhesive layer 12 and the film 13 for protective film formation is more favorable. Here, "the size of the unbonded region 92 (interlayer distance)" means "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 (the above-mentioned interlayer distance) of the unbonded region 92 is the same as the maximum value (size) of the above-mentioned interlayer distance of the above-mentioned unbonded region 91, preferably 0.5 μm or less, for example, 0.4 μm or less, 0.3 μm or less, Either of 0.2 μm or less and 0.1 μm or less.

The size (distance between layers) of the unbonded region 92 can be obtained in the same way as the size (distance between layers) of the above-mentioned unbonded region 91, except that the target double-layer combination is different.

The composite sheet 1A for protective film formation may not exist the non-bonding area|region 92 at all.

On the other hand, as described above, if the unevenness of the first surface 12a of the adhesive layer 12 is reduced, the thickness T _p of the film 13 for forming a protective film is not constant, but depends on the thickness Tp of the film 13 for forming a protective film (adhesive layer 12). There will be changes in the position, but the range of changes is very small.

Furthermore, as described above, if the unevenness of the first surface 12a of the adhesive layer 12 is reduced, the surface (second surface) 13b of the film 13 for forming a protective film on the side facing the adhesive layer 12 is smooth, or the unevenness is reduced. . Therefore, the appearance of the film 13 for protective film formation is not impaired. Therefore, if the protective film is formed from the film 13 for forming the protective film, the surface (second surface) of the formed protective film on the side facing the adhesive layer 12 can still be smooth, or the unevenness can be reduced, without damaging the appearance of the protective film. . Accordingly, in the composite sheet 1A for protective film formation, both the thin film 13 for protective film formation and a protective film can be excellent in design property.

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

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

Here, the composite sheet for forming a protective film 1A is taken as an example, and the adhesive layer and the film for forming a protective film are described. However, the protection of the composite sheet for forming a protective film 1B, the composite sheet for forming a protective film 1C, etc. In the case of the composite sheet for film formation, the adhesive layer and the film for protective film formation are the same.

In the composite sheet for forming a protective film of the present invention, the thickness (for example, T _p ) of the thin film for forming a protective film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and most preferably 5 to 50 μm. When the thickness of the thin film for protective film formation is more than the said lower limit, the protective film of higher protective ability can be formed. When the thickness of the film for protective film formation is below the said upper limit, thickness is suppressed from becoming too thick.

When the thickness of the film for forming a protective film varies depending on the position of the film for forming a protective film, the minimum thickness of the film for forming a protective film may be more than the above lower limit, and the thickness of the film for forming a protective film The maximum value may be below the above-mentioned upper limit value.

In addition, the "thickness of the film for forming a protective film" refers to the thickness of the film for forming a protective film as a whole. For example, the thickness of a film for forming a protective film composed of multiple layers refers to the thickness of all the layers constituting the film for forming a protective film. total thickness.

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

For example, using the method described above, a test piece is cut from a plurality of places (for example, 5 places) of the composite sheet for forming a protective film, and the minimum and maximum thickness values of the film for forming a protective film are obtained for the test piece, and then obtained from When calculating the average value of the minimum value and the average value of the maximum value of these numerical values, the average value of the above-mentioned minimum value can be more than the lower limit value of the thickness of the film for forming a protective film, and the average value of the above-mentioned maximum value can be obtained in the film for forming a protective film. below the upper limit of thickness.

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

The coating of the protective forming composition can be carried out by a known method, for example, using an air knife coater, a knife coater, a bar coater, a gravure coater, a roll coater, or a roll knife coater. , curtain coater, die coater, knife coater, screen coater, Mailer rod coater, kiss coater and other coating machine methods.

The drying conditions of the composition for forming a protective film are not particularly limited, but when the composition for forming a protective film contains a solvent described later, it is preferable to dry it by heating. On the other hand, the composition for forming a protective film containing a solvent is preferably dried at, 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 cured by heat.

Hereinafter, the thin film for protective film formation and the composition for protective film formation are demonstrated in detail by kind.

○Films for thermosetting protective film formation Preferable 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 polymerizing a polymerizable compound. The thermosetting component (B) is a component capable of performing a curing (polymerization) reaction using heat as a reaction trigger. In addition, the polymerization reaction in the present invention also includes polycondensation reaction.

After the film for forming a thermosetting protective film is attached to the back surface of the semiconductor wafer, the curing conditions for thermal curing are not particularly limited, provided that the cured product has a degree of hardening that fully exerts its functions. The type of film for forming a thermosetting protective film is 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 most preferably 120 to 170°C. On the other hand, the heating time during the above curing is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and most preferably 1 to 2 hours.

<Thermosetting protective film forming composition (III-1)> Preferable compositions for forming a thermosetting protective film include, for example, 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)") and the like.

[polymer component (A)] The polymer component (A) is a component for imparting film formability, flexibility, and the like to the film for forming a thermosetting protective film. The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. In the case of two or more types, the combination thereof and The ratio can be chosen arbitrarily.

Examples of the polymer component (A) include acrylic resins, polyesters, urethane resins, urethane acrylate resins, silicone resins, rubber resins, phenoxy resins, and thermosetting polymers. Amide, etc., preferably acrylic resin.

The above-mentioned acrylic resin in the polymer component (A) includes known acrylic polymers. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of an acrylic resin is more than the said lower limit, the shape stability (time-dependent stability at the time of storage) of the film for thermosetting protective film formation will improve. In addition, when the weight average molecular weight of the acrylic resin is below the above-mentioned upper limit, the thin film for forming a thermosetting protective film will easily follow the uneven surface of the adherend, and the adhesion between the adherend and the thermosetting protective film will be further suppressed. Voids and the like occur between films.

In this specification, the "weight average molecular weight" refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC) unless otherwise specified.

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 hardened film for forming a protective film (that is, the protective film) and the support sheet is suppressed, so that the peelability of the support sheet is moderately improved. Moreover, when Tg of an acrylic resin is below the said upper limit, the adhesive force between the film for thermosetting protective film formation and the to-be-adhered body of a protective film improves. In addition, not limited to acrylic resins, resin Tg systems in this specification, for example, use a differential scanning calorimeter (DSC), set the heating rate or cooling rate to 10°C/min, and make the temperature of the measurement object range from -70°C to 150°C. The change between ℃ can be obtained by confirming the inflection point.

Acrylic resins can be, for example, 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, a copolymer of two or more monomers is selected.

The above-mentioned (meth)acrylate constituting the acrylic resin includes, 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, (meth)acrylate base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid n-nonyl, 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 (palm (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group of the base ester is a chain structure (meth)acrylic acid alkyl ester with 1 to 18 carbon atoms; Cycloalkyl (meth)acrylates such as isocamphoryl (meth)acrylate and dicyclopentanyl (meth)acrylate; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; Cycloalkenyloxyalkyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate; (meth)acrylic imide; Glycidyl (meth)acrylate and other glycidyl-containing (meth)acrylates; Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid -2-Hydroxybutyl, (meth)acrylate-3-hydroxybutyl, (meth)acrylate-4-hydroxybutyl and other hydroxyl-containing (meth)acrylates; (Meth)acrylic acid-N-methylaminoethyl ester and other (meth)acrylates containing substituted amino groups. The term "substituted amino group" herein refers to a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.

Acrylic resins, for example, in addition to the above-mentioned (meth)acrylates, can also be made of (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide. One or two or more monomers are selected and copolymerized.

The monomer system constituting 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 thereof can be selected arbitrarily.

The acrylic resin may have functional groups capable of bonding with other compounds such as vinyl groups, (meth)acryl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups, for example. The above-mentioned functional groups of the acrylic resin may be bonded to other compounds through a crosslinking agent (F) described later, or may be directly bonded to other compounds without passing through a crosslinking agent (F). When the acrylic resin is bonded to other compounds using the above-mentioned functional group, there is a tendency to improve the reliability of the package obtained using the composite sheet for forming a protective film.

In the present invention, the polymer component (A) may be a thermoplastic resin other than an acrylic resin (hereinafter also referred to as "thermoplastic resin") alone or in combination without using an acrylic resin. 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 can easily follow the uneven surface of the adherend. Voids and the like are generated between the thin films for forming a protective film.

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

The aforementioned thermoplastic resins include, for example, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, and the like.

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 may be two or more kinds. In the case of two or more kinds, the combination and ratio thereof are Optional.

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) in the film for forming a thermosetting protective film), Regardless of the type of polymer component (A), it is preferably 5-85% by mass, more preferably 5-75% by mass, for example, 5-65% by mass, 5-50% by mass, and 10-35% by mass any of these.

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

[Thermosetting component (B)] The thermosetting component (B) is a component for hardening the thin film for thermosetting protective film formation. The thermosetting component (B) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. In the case of two or more types, the combination The ratio can be chosen arbitrarily.

The thermosetting component (B) can be for example: epoxy thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, polysiloxane resin, etc., preferably epoxy thermosetting resin resin.

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

・Epoxy resin (B1) Epoxy resins (B1) include known ones, for example: polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrides, o-cresol novolac epoxy resins, dicyclopentanyl Diene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and other epoxy 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 between epoxy resins with unsaturated hydrocarbon groups and 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 a semiconductor wafer with a protective film obtained using a composite sheet for forming a protective film can be improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include, for example, a compound in which part of the epoxy group of a polyfunctional epoxy resin is converted to a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by adding (meth)acrylic acid or its derivatives to an epoxy group. In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin, and the like. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples include: vinyl (ethenyl group), 2-propenyl (allyl), (meth)acryl, (meth)acryl Amino group, etc., preferably acryl group.

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

In this specification, the "number average molecular weight" refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC) unless otherwise specified.

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

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

・Thermosetting agent (B2) The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1). Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. The above-mentioned functional groups can be, for example, phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and acid-anhydrided groups from acid groups, etc., preferably phenolic hydroxyl groups, amino groups, or acid-anhydrided groups from acid groups. A group, more preferably a phenolic hydroxyl group or an amine group.

Among the thermosetting agents (B2), phenolic curing agents having phenolic hydroxyl groups include, for example, polyfunctional phenolic resins, biphenyls, novolak-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Phenolic resin etc. Among the thermosetting agents (B2), examples of the amine-based curing agent having an amino group include dicyandiamine and the like.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group. The thermosetting agent (B2) having an unsaturated hydrocarbon group can be, for example, a compound in which some of the hydroxyl groups of a phenol resin are substituted by a group having an unsaturated hydrocarbon group, and a compound formed by directly bonding an aromatic ring of the phenol resin to a group having an unsaturated hydrocarbon group. formed compounds, etc. The above-mentioned unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

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

In the thermosetting agent (B2), the number average molecular weight of the resin components such as polyfunctional phenol resin, novolac type phenol resin, dicyclopentadiene type phenol resin, aralkyl type phenol resin, etc. is preferably 300~30000 , The best series is 400~10000, and the best series is 500~3000. In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenyl and dicyandiamide is not particularly limited, and is preferably 60-500, for example.

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

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass relative to 100 parts by mass of the content of the epoxy resin (B1) , More preferably, it is 1-200 parts by mass, and may be any one of 1-100 parts by mass, 1-50 parts by mass, 1-25 parts by mass, and 1-10 parts by mass. When the said content of a thermosetting agent (B2) is more than the said lower limit, hardening of the thin film for thermosetting protective film formation progresses more easily. In addition, when the above-mentioned content of the thermosetting agent (B2) is below the above-mentioned upper limit, the moisture absorption rate of the film for forming a thermosetting protective film is reduced, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved. .

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) relative to The content of the polymer component (A) is 100 parts by mass, preferably 20-500 parts by mass, more preferably 30-300 parts by mass, especially 40-150 parts by mass, for example, 45-100 parts by mass, and 50-300 parts by mass. Any one of 80 parts by mass. When the content of the thermosetting component (B) is within such a range, for example, the adhesive force between the hardened film for forming a protective film and the support sheet is suppressed, and the peelability of the support sheet is improved.

[Hardening Accelerator (C)] The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening speed of the composition (III-1). Preferred hardening accelerators (C) can include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and ginseng (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles in which more than one hydrogen atom is replaced by a group other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (more than one hydrogen atom is replaced by an organic group) Substituted phosphine); Tetraphenylphosphonium tetraphenyl borate, triphenylphosphine tetraphenyl borate, tetraphenyl borate, etc.

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

When the curing accelerator (C) is used, in the composition (III-1) and the film for forming a thermosetting protective film, the content of the curing accelerator (C) is 100% relative to the content of the thermosetting component (B). Parts by mass are preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass. When the said content of a hardening accelerator (C) is more than the said lower limit, the effect by using a hardening accelerator (C) can be made more remarkable. Moreover, when the content of the hardening accelerator (C) is below the above-mentioned upper limit, for example, it is possible to improve the inhibition 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 medium segregation moving toward the interface with the adherend further improves the reliability of the semiconductor wafer with protective film obtained by using the composite sheet for forming protective film.

[Filler (D)] The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). When the film for forming a thermosetting protective film contains the filler (D), it is possible to more easily adjust the above-mentioned water absorption rate and adhesive force change rate within the target range. In addition, by containing the filler (D) in the film for forming a thermosetting protective film and the protective film, the coefficient of thermal expansion can be adjusted more easily. Optimizing the target will further enhance the reliability of the semiconductor wafer with protective film obtained by using the composite sheet for forming protective film. Moreover, when the film for thermosetting protective film formation contains a filler (D), the moisture absorption rate of a protective film can also be reduced, and heat dissipation property etc. can be improved.

The filler (D) may be either an organic filler or an inorganic filler, and is preferably an inorganic filler. Preferred inorganic fillers include powders such as silicon dioxide, alumina, talc, calcium carbonate, titanium dioxide, red iron oxide, silicon carbide, and boron nitride; balls made by spheroidizing these inorganic fillers ; surface modifiers of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silica or alumina, more preferably silica.

The filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type or two or more types. If there are two or more types, the combination and ratio The system 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 filling of the thermosetting protective film forming film) Material (D) content), preferably 5-80% by mass, more preferably 10-70% by mass, for example, any of 20-65% by mass, 30-65% by mass and 40-65% by mass one. When the content of the filler (D) is within such a range, the above-mentioned coefficient of thermal expansion can be adjusted more easily, and the strength of the film for forming a protective 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 use of the coupling agent (E) having a functional group capable of reacting with an inorganic compound or an organic compound can improve the adhesion and adhesion of the thermosetting protective film forming film to the adherend. In addition, by using the coupling agent (E), the water resistance of the cured product (protective film) of the thin film for forming a thermosetting protective film can be improved without impairing the heat resistance.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with the functional groups of the polymer component (A) and the thermosetting component (B), more preferably a silane coupling agent. Preferred above-mentioned silane coupling agents can be for example: 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-mercaptopropane Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfonamide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, ethylene triacetyloxysilane, 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 type, or two or more types. In the case of two or more types, the combination and ratio The system can be selected arbitrarily.

In the case of using the coupling agent (E), in the composition (III-1) and the film for forming a thermosetting protective film, the content of the coupling agent (E) is relative to the polymer component (A) and the thermosetting component ( The total content of B) is 100 parts by mass, preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and most preferably 0.1 to 5 parts by mass. When the above-mentioned content of the coupling agent (E) is more than the above-mentioned lower limit value, the dispersibility of the filler (D) to the resin is improved, the adhesiveness between the film for forming a thermosetting protective film and the adherend is improved, etc., The effect resulting from the use of the coupling agent (E) can be made more pronounced. Moreover, when the said content of a coupling agent (E) is below the said upper limit, generation|occurrence|production of outgassing is further suppressed.

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

The crosslinking agent (F) can be exemplified for example: organic polyvalent isocyanate compound, organic polyimine compound, metal chelate crosslinking agent (crosslinking agent with metal chelate structure), aziridine crosslinking agent (with Aziridine-based cross-linking agent), etc.

The above-mentioned organic polyvalent isocyanate compounds include, for example: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter these compounds are collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); the above-mentioned aromatic polyvalent isocyanate compounds Trimers, isocyanurates, and adducts of compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the above-mentioned aromatic polyvalent isocyanate compounds, etc., with polyol compounds, etc. The above-mentioned "addition body" refers to the above-mentioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Reaction products containing low molecular weight active hydrogen compounds. Examples of the above-mentioned adducts include trimethylolpropane-diisocyanate xylylene adducts, which will be described later, and the like. Also, the "isocyanate-terminated urethane prepolymer" is as described above.

The above-mentioned organic polyvalent isocyanate compounds can be more systematically for example: 2,4-cresyl diisocyanate; 2,6-cresyl diisocyanate; 1,3-xylylene diisocyanate; 1, 4-Xylene diisocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-Methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Alone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; Compounds of any one or two or more of cresyl isocyanate, hexamethylene diisocyanate, and xylylene diisocyanate; lysine diisocyanate, etc.

The above-mentioned organic polyimine compounds can be, for example: N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridine N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine Wait.

When the crosslinking agent (F) is an organic polyvalent isocyanate compound, the polymer component (A) is preferably a hydroxyl-containing polymer. When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the reaction between the cross-linking agent (F) and the polymer component (A) can easily protect A crosslinked structure is introduced into the film for film formation.

The crosslinking agent (F) 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. In the case of two or more kinds, the combination thereof and The ratio can be chosen arbitrarily.

When using the crosslinking agent (F), the content of the crosslinking agent (F) in the composition (III-1) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the polymer component (A). 0.1-10 parts by mass, more preferably 0.1-10 parts by mass, and especially 0.5-5 parts by mass. When the said content of a crosslinking agent (F) is more than the said lower limit, the effect by using a crosslinking agent (F) can be made more remarkable. Moreover, when the said content of a crosslinking agent (F) is below the said upper limit, excessive use of a crosslinking agent (F) can be suppressed.

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

The energy ray curable resin (G) is obtained by polymerizing (curing) an energy ray curable compound. The aforementioned energy ray-curable compound includes a compound having at least one polymerizable double bond in one molecule, preferably an acrylate compound having a (meth)acryl group.

The above-mentioned acrylate-based compounds can be, for example: trimethylolpropane tri[(meth)acrylate], tetramethylolmethane tetra[(meth)acrylate], neopentylthritol tri[(meth)acrylate] Acrylates], Neopentylthritol Tetra[(meth)acrylate], Dineopentylthritol Monohydroxypenta[(meth)acrylate], Dineopentylthritol Hexa[(meth)acrylate], 1,4-butanediol di[(meth)acrylate], 1,6-hexanediol di[(meth)acrylate] and other (meth)acrylates containing chain aliphatic skeleton; di( Cyclic aliphatic skeleton-containing (meth)acrylates such as dicyclopentanyl methacrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di[(meth)acrylate]; oligomer Ester (meth)acrylate; Urethane (meth)acrylate oligomer; Epoxy modified (meth)acrylate; Polyether (meth)acrylate other than the above-mentioned polyalkylene glycol (meth)acrylate Base) acrylates; itaconic acid oligomers, etc.

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

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

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

When the energy ray-curable resin (G) is used, the content of the energy ray-curable resin (G) in the composition (III-1) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, 10~85% by mass of extra-fine.

[Photopolymerization initiator (H)] When the composition (III-1) contains the energy ray curable resin (G), in order to efficiently carry out the polymerization reaction of the energy ray curable resin (G), it may also contain a photopolymerization initiator (H) .

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。The photopolymerization initiator (H) in the composition (III-1) can include, for example: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether , benzoin benzoic acid, benzoin benzoic acid methyl ester, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1- Acetophenone compounds such as ketones and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide , 2,4,6-trimethylbenzoyl diphenylphosphine oxide and other acylated phosphine oxide compounds; benzyl phenyl sulfide, tetramethylamine thioformyl monosulfide and other sulfide compounds; 1-hydroxycyclohexyl α-ketol compounds such as benzophenone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; oxygen sulfur 𠮿

isosulfur

Compounds; peroxy compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; diphenyl ketone; 2,4-diethyloxysulfurium

; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone, etc. Furthermore, the above-mentioned photopolymerization initiator may still include, for example: quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines; and the like.

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 thereof can be selected arbitrarily.

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

[Color (I)] The composition (III-1) and the film for forming a thermosetting protective film may contain a colorant (I). As a coloring agent (I), known things, such as an inorganic pigment, an organic pigment, and an organic dye, are mentioned, for example.

Examples of the above-mentioned organic pigments and organic dyes include ammonium pigments, cyanine pigments, merocyanine pigments, croconium pigments, and squarylium pigments. (squarylium)-based pigments, azulenium-based pigments, polymethine-based pigments, naphthoquinone-based pigments, pyrylium-based pigments, phthalocyanine-based pigments, naphthalene Phthalocyanine dyes, naphthalactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene (Perylene)-based pigments, dioxazine-based pigments, quinacridone-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, and pyrrole-based pigments , thioindigo pigments, metal complex pigments (metal complex salt dyes), dithiol metal complex pigments, indole phenol pigments, triallyl methane Triallyl methane-based pigments, anthraquinone-based pigments, dioxazine-based pigments, naphthol-based pigments, azomethine-based pigments, benzimidazolone-based pigments, pyranthracene Ketone (pyranthrone) pigments and shrene (threne) pigments, etc.

Examples of the above-mentioned inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO ( Indium tin oxide) based pigments, ATO (antimony tin oxide) based pigments, 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 there are two or more kinds, the combination and ratio thereof The system can be chosen arbitrarily.

In the case of using the colorant (I), the content of the colorant (I) in the film for forming a thermosetting protective film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the coloring agent (I) in the thermosetting protective film-forming film to adjust the light transmittance of the protective film, marking visibility when laser marking is performed on the protective film can be adjusted. Moreover, by adjusting the content of the coloring agent (I) in the film for forming a thermosetting protective film, the designability of the protective film can be improved, and grinding marks on the back surface of the semiconductor wafer can be made less visible. Considering this point, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all components other than the solvent (that is, the colorant (I) of the film for forming a thermosetting protective film content), preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and most preferably 0.1 to 5% by mass. When the said content of a coloring agent (I) is more than the said lower limit, the effect by using a coloring agent (I) can be made more remarkable. Moreover, when the said content of a coloring agent (I) is below the said upper limit, the excessive fall of the light transmittance of the film for thermosetting protective film formation is suppressed.

[General additive (J)] The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) within the range not to impair the effect of the present invention. General-purpose additives (J) can be known, and can be selected arbitrarily according to the purpose, and are not particularly limited. Preferred examples include: plasticizers, antistatic agents, antioxidants, gettering agents, etc. .

The general-purpose additive (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio The system 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] The composition (III-1) preferably further contains a solvent. The solvent-containing composition (III-1) showed good handling properties. The above-mentioned solvents are not particularly limited, and preferred systems can include, for example: hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-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 thereof can be selected arbitrarily.

The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint of more uniform mixing of the components contained in the composition (III-1).

＜＜Method for producing thermosetting protective film forming composition＞＞ A composition for forming a thermosetting protective film such as composition (III-1) can be obtained by blending the respective components constituting it. The order of addition of the respective components is not particularly limited, and two or more components may be added simultaneously. When using a solvent, the solvent can be mixed with any blending ingredient other than the solvent, and then the blended ingredient can be used after pre-diluted, or it can be in a state where no blending ingredient other than the solvent is pre-diluted Next, the solvent is mixed with these blending ingredients. When blending, the method of mixing the components is not particularly limited, for example: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing by using a mixer; a method of mixing by applying ultrasonic waves. Appropriately select among other known methods. The temperature and time during the addition and mixing of each component are not specifically limited on the premise that the components will not deteriorate, as long as they are properly adjusted, the temperature is preferably 15~30°C.

○Films for forming energy ray curable protective films The thin film for forming an energy ray curable protective film includes those containing the energy ray curable component (a), preferably containing the energy ray curable component (a) and a filler. In the film for forming an energy ray curable protective film, the energy ray curable component (a) is preferably uncured, preferably has adhesiveness, more preferably is uncured and has adhesiveness. The so-called "energy line" and "energy line hardening" here are the same as the previous explanation.

After attaching the thin film for forming an energy ray curable protective film to the back surface of the semiconductor wafer, the curing conditions for curing are not particularly limited on the premise that the cured product has a degree of curing sufficient to fully perform its functions. What is necessary is just to select suitably according to the kind of thin film for energy ray curable protective film formation. 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 . However, in the above hardening, the luminous flux of the energy line is preferably 100 to 1000 mJ/cm ² .

<Energy ray curable protective film forming composition (IV-1)> A preferable 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 aforementioned energy ray curable component (a) (also abbreviated as "composition (IV-1)") and the like.

[energy ray hardening ingredient (a)] The energy ray curable component (a) is a component that can be cured by energy ray irradiation, and is also used to impart film-forming properties, flexibility, etc. to the film for forming an energy ray curable protective film, and to form a hard protective film after curing ingredients used. The energy ray curable component (a) includes, for example: 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 above-mentioned polymer (a1) may be at least partially cross-linked by a cross-linking agent, or may not be cross-linked.

(Polymer (a1) having an energy ray hardening group and a weight average molecular weight of 80,000 to 2,000,000) Examples of the polymer (a1) having an energy ray hardening group and a weight-average molecular weight of 80,000 to 2,000,000 include an acrylic polymer (a11) having a functional group capable of reacting with groups in other compounds, and having a An acrylic resin (a1-1) produced by reacting an energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond with a reactive group of the above-mentioned functional group.

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

・Acrylic polymer with functional groups (a11) The acrylic polymer (a11) having the above-mentioned functional group can be, for example, one formed by copolymerization of an acrylic monomer having the above-mentioned functional group and 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 above-mentioned acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method may be used for the polymerization method.

The acrylic monomers having the above functional groups include, for example, hydroxyl-containing monomers, carboxyl-containing monomers, amine-containing monomers, substituted amino-containing monomers, epoxy-containing monomers, and the like.

The above-mentioned hydroxyl-containing monomer system can be exemplified: (meth) hydroxymethyl acrylate, (meth) acrylate-2-hydroxyethyl, (meth) acrylate-2-hydroxypropyl, (meth) acrylate-3 -Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates ; Non-(meth)acrylic unsaturated alcohols (unsaturated alcohols without a (meth)acryl skeleton) such as vinyl alcohol and allyl alcohol.

The above-mentioned carboxyl group-containing monomer system can be exemplified for example: (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids with ethylenically unsaturated bonds); fumaric acid, itaconic acid, cis Butenedioic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the above-mentioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. Carboxyalkyl (meth)acrylate and the like.

The above-mentioned acrylic monomers having functional groups are preferably hydroxyl-containing monomers.

The acrylic monomers constituting the above-mentioned acrylic polymer (a11) and having the above-mentioned functional groups may be only one type, or two or more types. In the case of two or more types, the combination and ratio can be selected arbitrarily. .

The acrylic monomer system without the above-mentioned functional groups can be exemplified: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl methacrylate, 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 Methacrylate, Myristyl (Meth)acrylate (Myristyl (Meth)acrylate), Pentadecyl (Meth)acrylate, Hexadecyl (Meth)acrylate Alkyl esters (palm (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. Alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms, etc.

Furthermore, acrylic monomers without the above-mentioned functional groups include, for example: methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate (meth)acrylates containing alkoxyalkyl groups such as esters, ethoxyethyl (meth)acrylates, etc.; aryl (meth)acrylates containing phenyl (meth)acrylates, etc. and having aromatic groups ( Meth)acrylates; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylate-N,N-dimethylaminoethyl ester, (meth)acrylate-N,N-di (Meth)acrylates having non-crosslinkable tertiary amino groups, such as methamidopropyl ester, etc.

The acrylic monomers constituting the above acrylic polymer (a11) and not having the above functional groups may be only one type, or two or more types. In the case of two or more types, the combination and ratio can be arbitrary choose.

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

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

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

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

・Energy ray hardening compound (a12) In the energy ray-curable compound (a12), the group capable of reacting with the functional group of the acrylic polymer (a11) preferably has 1 selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group. One or two or more, more preferably the above-mentioned group has an isocyanate group. The above-mentioned energy ray-curable compound (a12) is, for example, when the above-mentioned group has an isocyanate group, and the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having the above-mentioned functional group as a hydroxyl group.

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

Examples of the energy ray-curing compound (a12) include: 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryl isocyanate , Allyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate; Acryl monoisocyanate compounds obtained by reacting diisocyanate compounds or polyisocyanate compounds with hydroxyethyl (meth)acrylate; Acryl monoisocyanate compounds obtained by reacting diisocyanate compounds or polyisocyanate compounds, polyol compounds, and hydroxyethyl (meth)acrylate, etc. Among these, the energy ray-curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.

The aforementioned energy ray-curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be one type, or two or more types. In the case of two or more types, the combination and ratio thereof can be selected arbitrarily. .

In the acrylic resin (a1-1), the content of the energy ray-curable group derived from the energy ray-curable compound (a12) relative to the functional group derived from the acrylic polymer (a11) The proportion of the content of the preferred is 20-120 mol%, more preferably 35-100 mol%, and the most preferred is 50-100 mol%. When the ratio of the above-mentioned content is within such a range, the adhesive force of the cured protective film becomes larger. In addition, when the above-mentioned energy ray-curable compound (a12) is a monofunctional compound (the above-mentioned group has only one in 1 molecule), the upper limit of the ratio of the above-mentioned content is 100 mol%, but when the above-mentioned energy When the line-curing compound (a12) is a polyfunctional compound (having two or more of the above-mentioned groups in one molecule), the upper limit of the above-mentioned content exceeds 100 mol%.

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

When the above-mentioned polymer (a1) is at least partly cross-linked by a cross-linking agent, the above-mentioned polymer (a1) may not belong to any of the above-mentioned units described for constituting the above-mentioned acrylic polymer (a11). body, and may be polymerized from a monomer having a group that reacts with the crosslinking agent, and the one that is crosslinked at the group that will react with the above crosslinking agent may be the above energy ray curable compound (a12) A group derivatized that reacts with the above-mentioned functional group to perform cross-linking.

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

(Compound (a2) having an energy ray hardening 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, preferably (meth)acryl, ethylene Base etc.

The above-mentioned compound (a2) is not particularly limited as long as the above-mentioned conditions are met, for example: a low molecular weight compound with an energy ray curable group, an epoxy resin with an energy ray curable group, an epoxy resin with an energy ray curable group phenolic resin, etc.

Among the above compounds (a2), the low-molecular-weight compound having an energy-ray-curable group includes polyfunctional monomers or oligomers, and is preferably an acrylate compound having a (meth)acryl group. The above-mentioned acrylate compounds can be exemplified as: 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di[(meth)acrylate], propoxylated ethylene Oxylated bisphenol A bis[(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) Acryloxyethoxy)phenyl] terpene, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di[(methyl) acrylate], 1,10-decanediol di[(meth)acrylate], 1,6-hexanediol di[(meth)acrylate], 1,9-nonanediol di[(meth)acrylate], 1,9-nonanediol di[(meth)acrylate] ) acrylate], dipropylene glycol di[(meth)acrylate], tripropylene glycol di[(meth)acrylate], polypropylene glycol di[(meth)acrylate], polybutylene glycol di[(meth)acrylate], polybutylene glycol di[(meth)acrylate], base) acrylate], ethylene glycol bis[(meth)acrylate], diethylene glycol bis[(meth)acrylate], triethylene glycol bis[(meth)acrylate], 2,2 - Bis[4-((meth)propenyloxyethoxy)phenyl]propane, neopentyl glycol di[(meth)acrylate], ethoxylated polypropylene glycol di[(meth)acrylate ], 2-hydroxy-1,3-di(meth)acryloxypropane and other difunctional (meth)acrylates; Isocyanuric acid ginseng [2-(meth)acryloxyethyl], ε-caprolactone modified isocyanuric acid ginseng [2-(meth)acryloxyethyl], ethoxy Triglycerol tri[(meth)acrylate], Neopentylthritol tri[(meth)acrylate], Trimethylolpropane tri[(meth)acrylate], Di(trimethylolpropane) tetra [(meth)acrylates], ethoxylated neopentylthritol tetrakis[(meth)acrylates], neopentylthritol tetrakis[(meth)acrylates], dipenteoerythritol poly(meth)acrylates ) acrylate, diperythritol hexa(meth)acrylate and other multifunctional (meth)acrylates; Polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers, etc.

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

The weight average molecular weight of the above compound (a2) is preferably 100-30000, more preferably 300-10000.

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. In the case of two or more kinds, the combination thereof and The ratio can be chosen arbitrarily.

[Polymer (b) without energy ray hardening group] 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 above compound (a2), it may further contain a polymer having no energy ray curable group (b) is preferred. The above-mentioned polymer (b) may be at least partially cross-linked by a cross-linking agent, or may not be cross-linked.

Examples of the polymer (b) having no energy-ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and urethane acrylate resins. Among these, the above-mentioned polymer (b) is preferably an acrylic polymer (hereinafter also referred to as "acrylic polymer (b-1)").

The acrylic polymer (b-1) can be a known thing, for example: it can be a single polymer of a single acrylic monomer, or it can be a copolymer of two or more acrylic monomers, or it can be made of one or more A copolymer of two or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).

The above-mentioned acrylic monomers constituting the acrylic polymer (b-1) are, for example, alkyl (meth)acrylates, (meth)acrylates with a ring skeleton, glycidyl-containing ( Meth)acrylate, hydroxyl group-containing (meth)acrylate, substituted amino group-containing (meth)acrylate, etc. Here, the so-called "substituted amino group" is as described above.

The above-mentioned alkyl (meth)acrylates can be, for example: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate Base) n-butyl acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (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), (meth)acrylate base) tridecyl acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate ester (palm (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. Alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms.

The above-mentioned (meth)acrylates having a cyclic skeleton can be, for example, cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; Dicyclopentenyloxyethyl (meth)acrylate, etc., cycloalkenyloxyalkyl (meth)acrylate, etc., etc.

As for the (meth)acrylate containing a glycidyl group, glycidyl (meth)acrylate etc. are mentioned, for example. The above-mentioned (meth)acrylates containing hydroxyl groups can be, for example: methylol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate Base) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the (meth)acrylates containing a substituted amino group include N-methylaminoethyl (meth)acrylate.

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

The above-mentioned polymer (b) without energy ray hardening group after at least a part of it is cross-linked by a cross-linking agent is, for example, produced by the reactive functional group in the above-mentioned polymer (b) and a cross-linking agent. React to the latter. The above-mentioned reactive functional group is not particularly limited as long as it is properly selected according to the type of crosslinking agent and the like. For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional groups include hydroxyl groups, carboxyl groups, and amino groups. Among these, hydroxyl groups with high reactivity with isocyanate groups are preferred. Also, when the crosslinking agent is an epoxy-based compound, examples of the reactive functional group include carboxyl, amine, and amide groups, among which carboxyl having high reactivity with epoxy is preferred. However, from the viewpoint of preventing corrosion of semiconductor wafers and circuits of semiconductor wafers, the above-mentioned reactive functional groups are preferably groups other than carboxyl groups.

The aforementioned polymer (b) having a reactive functional group without an energy ray curable group includes one obtained by polymerizing a monomer having at least the aforementioned reactive functional group. In the case of the acrylic polymer (b-1), any one or both of the above-mentioned acrylic monomers and non-acrylic monomers listed for the monomers constituting it are used as having the above-mentioned reactive functional group Those who can. The above-mentioned polymer (b) having a reactive functional group having a hydroxyl group includes, for example, one obtained by polymerizing a hydroxyl-containing (meth)acrylate. In addition, the above-mentioned Among acrylic monomers or non-acrylic monomers, one or more hydrogen atoms are replaced by the above-mentioned reactive functional groups, which are obtained by polymerization.

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

The weight average molecular weight (Mw) of the polymer (b) without an energy ray-curable group is preferably 10,000 to 2,000,000, more preferably 100000~1500000. The so-called "weight average molecular weight" here is as described above.

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

The composition (IV-1) includes one or both of the above-mentioned polymer (a1) and the above-mentioned compound (a2). However, when the composition (IV-1) contains the above-mentioned compound (a2), it is preferable to further contain the polymer (b) not having an energy ray curable group. 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 above-mentioned polymer (a1), the above-mentioned compound (a2) and the polymer (b) without an energy ray curable group, in the composition (IV-1), the above-mentioned compound The content of (a2) is preferably 10 to 400 parts by mass, more preferably 30 parts by mass based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) not having an energy ray hardening group. ~350 parts by mass.

In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) without an energy ray-curable group to the total content of the components other than the solvent (i.e. , the total content of the energy ray curable component (a) and the polymer (b) without energy ray curable group in the film for forming an energy ray curable protective film), preferably 5 to 90% by mass, Better is 10-80% by mass, and Extra-best is 20-70% by mass. When the above-mentioned ratio of the content of the energy ray curable component is within such a range, the energy ray curability of the thin film for forming an energy ray curable protective film can be further improved.

Composition (IV-1) is not only the above-mentioned energy ray curable components, but also can contain thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants and general additives for compounding purposes. Select 1 or 2 or more types in the composition 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 film for forming an energy ray curable protective film to an adherend by heating can be improved, In addition, 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 an energy ray curable component and a colorant, the formed thin film for forming an energy ray curable protective film can exhibit the same thermosetting protective film as 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, colorants and general additives of the composition (IV-1) are respectively exemplified by the thermosetting components of the composition (III-1). The same thing as the property component (B), the filler (D), the coupling agent (E), the crosslinking agent (F), the photopolymerization initiator (H), the colorant (I) and the general additive (J).

In the composition (IV-1), each of the above-mentioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives may be used alone or in combination of two or more , if two or more cases are used, the combination and ratio can be chosen arbitrarily.

The content of the above-mentioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants and general additives in the composition (IV-1) can be adjusted as long as it suits the purpose. There is no particular limitation.

Composition (IV-1) preferably further contains a solvent because the handling property can be improved by dilution. The solvent contained in the composition (IV-1) includes, for example, the same solvents as those of the above-mentioned composition (III-1). The solvent system contained in the composition (IV-1) may be only one kind, or may be two or more kinds.

＜<Manufacturing method of energy ray curable protective film forming composition>> The composition for forming an energy ray curable protective film such as the composition (IV-1) can be obtained by blending each component for constituting it. The order of addition of the respective components is not particularly limited, and two or more components may be added simultaneously. When using a solvent, the solvent can be mixed with any blending ingredient other than the solvent, and then the blended ingredient can be used after pre-diluted, or it can be used without pre-diluted any blended ingredient other than the solvent. , the solvent is mixed with these blending ingredients. When blending, the method of mixing the components is not particularly limited, for example: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing by using a mixer; a method of mixing by applying ultrasonic waves. Appropriately select among other known methods. The temperature and time during the addition and mixing of each component are not specifically limited on the premise that the components will not deteriorate, as long as they are properly adjusted, the temperature is preferably 15~30°C.

○Films for forming non-hardening protective films The aforementioned non-curable protective film-forming thin film does not exhibit characteristic changes due to curing, but in the present invention, the protective film is considered to have been formed at the stage of attaching to the target place such as the above-mentioned back surface of the semiconductor wafer.

As a preferable non-hardening protective film forming film, the thing containing a thermoplastic resin is mentioned, for example.

<Non-hardening protective film forming composition (V-1)> Examples of the composition system for forming a non-curable protective film include the composition (V-1) for forming a non-curable protective film containing the above-mentioned thermoplastic resin (also referred to as "composition (V-1)" in this specification). Wait.

[thermoplastic resin] The aforementioned thermoplastic resin is not particularly limited. More specifically, the above-mentioned thermoplastic resins include, for example, acrylic resins, polyesters, polyurethanes, phenoxy resins, polybutenes, polybutadienes, polystyrenes, etc. The same applies to non-hardening resins.

The thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be one kind or two or more kinds. In the case of two or more kinds, the combination and the ratio thereof are Optional.

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 in the film for forming a non-curable protective film) is preferably It is 5-90 mass %, for example, may be any of 10-80 mass %, 20-70 mass %, etc.

Composition (V-1) is not only the above-mentioned thermoplastic resin, but also contains one or two or more kinds selected from the group consisting of filler, coupling agent, crosslinking agent, coloring agent and general additives.

For example, by using the above-mentioned composition (V-1) containing a thermoplastic resin and a coloring agent, the formed film for forming a non-hardening protective film can exhibit the same color as that for forming a thermosetting protective film as described above. The same effect is obtained when the film contains the colorant (I).

The above-mentioned fillers, coupling agents, crosslinking agents, colorants and general additives in the composition (V-1) can be respectively listed as fillers (D), coupling agents (E), The crosslinking agent (F), the colorant (I) and the general additive (J) are the same.

In the composition (V-1), the above-mentioned 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, Its combination and ratio can be selected arbitrarily.

In the composition (V-1), the contents of the above-mentioned fillers, coupling agents, crosslinking agents, colorants and general additives are not particularly limited as long as they can be appropriately adjusted according to the purpose.

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

＜<Production method of non-hardening protective film forming composition＞＞ Compositions for forming a non-curable protective film such as the composition (V-1) can be obtained by blending each component constituting it. The order of addition of the respective components is not particularly limited, and two or more components may be added simultaneously. When using a solvent, the solvent can be mixed with any blending ingredient other than the solvent, and then the blended ingredient can be used after pre-diluted, or it can be used without pre-diluted any blended ingredient other than the solvent. , the solvent is mixed with these blending ingredients. When blending, the method of mixing the components is not particularly limited, for example: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing by using a mixer; a method of mixing by applying ultrasonic waves. Appropriately select among other known methods. The temperature and time during the addition and mixing of each component are not specifically limited on the premise that the blended components will not deteriorate, as long as they are properly adjusted, the temperature is preferably 15~30°C.

◎Other layers The above-mentioned supporting sheet may also include other layers such as the above-mentioned intermediate layer in addition to the base material and the adhesive layer within the range that does not impair the effect of the present invention. Furthermore, the above-mentioned composite sheet for forming a protective film may include other layers in addition to the base material, the adhesive layer, and the film for forming a protective film within the range that does not impair the effects of the present invention. The layer system can be the above-mentioned other layers included in the support sheet, and can also be configured in a state of not directly contacting the support sheet. The above-mentioned other layers can be selected arbitrarily according to the purpose, and the types are not particularly limited.

One embodiment of the support sheet and the protective film-forming composite sheet includes, for example, an adhesive layer that is non-energy ray curable, and the adhesive layer contains at least the above-mentioned The acrylic polymer and the crosslinking agent are contained in the adhesive layer in an amount of 0.3 to 50 parts by mass relative to 100 parts by mass of the above-mentioned acrylic polymer, and the above-mentioned content of the first surface of the substrate is The maximum height roughness (Rz) is 0.01~8μm.

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

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

An example of an embodiment of the support sheet and protective film-forming composite sheet includes: the adhesive layer is non-energy ray curable, and the adhesive layer contains at least The acrylic polymer and the crosslinking agent are contained in the adhesive layer in an amount of 0.3 to 50 parts by mass relative to 100 parts by mass of the acrylic polymer, and the acrylic polymer system has Constituent units derived from alkyl (meth)acrylates with an alkyl group having 4 or more carbon atoms and constituent units derived from hydroxyl-containing monomers. In the above-mentioned acrylic polymer, relative to the total amount of constituent units, the The content of the constituent units derived from the monomer is 1-35% by mass, the above-mentioned crosslinking agent is an isocyanate-based crosslinking agent, and the above-mentioned maximum height roughness (Rz) of the first surface of the substrate is 0.01-8 μm.

◇Manufacturing method of composite sheet for protective film formation The above composite sheet for forming a protective film is produced, for example, by the following production method (also referred to as "manufacturing method (S1)" in this specification) which includes: The step of producing a laminated sheet formed by laminating layers in its thickness direction (also referred to as "laminated sheet production step (1)" in this specification); and the step of storing the above-mentioned laminated sheet under pressure in its thickness direction (in this Also known as "Laminate Preservation Step"). The formation method of each layer (substrate, adhesive layer, and protective film forming film) is as described above. Hereinafter, the above-mentioned manufacturing method (S1) will be described in more detail according to each step.

◎Manufacturing method (S1) ＜＜Laminate production steps (1)＞＞ In the above-mentioned laminated sheet production step (1), a laminated sheet formed by laminating layers in the thickness direction in the order of the base material, the adhesive layer, and the film for forming a protective film is produced. In this step, for example, by laminating so as to correspond to the positional relationship of the above layers (base material, adhesive layer, protective film forming film, etc.), a laminated sheet having the same laminated structure as the target protective film forming composite sheet is produced. In addition, in this specification, the so-called "laminated sheet" refers to a laminated sheet having the same laminated structure as the target protective film forming composite sheet as described above, and the above-mentioned laminated sheet preservation step has not been performed unless otherwise specified.

For example, when laminating an adhesive layer on a base material in the production of a support sheet, it is only necessary to apply the above-mentioned adhesive composition on the base material and dry it if necessary.

On the other hand, for example, when a film for forming a protective film is further laminated on an adhesive layer that has been laminated on a base material, the protective film can be formed directly by coating the composition for forming a protective film on the adhesive layer. Use film. Layers other than the film for forming a protective film also use the composition for forming this layer, and this layer can be laminated on the adhesive layer by the same method. Accordingly, when any composition is used to form a continuous two-layer laminate structure, a new layer can be formed by further coating the composition on the layer formed by the above composition. However, the layer that is laminated after these two layers is preferably formed in advance using the above-mentioned composition on another release film, and then the exposed surface of the formed layer opposite to the side that is in contact with the above-mentioned release film is separated from the already formed layer. The exposed surfaces of the formed remaining layers are bonded to form a continuous two-layer laminate structure. In this case, it is preferable to coat the above-mentioned composition on the release-treated surface of the release film. The release film may be removed as necessary after the laminated structure is formed.

For example, when manufacturing a composite sheet for protective film formation in which an adhesive layer is laminated on a base material and a film for forming a protective film is laminated on the adhesive layer (the support sheet is a laminate of the base material and the adhesive layer) When using a composite sheet), the adhesive composition is applied on the substrate, and dried if necessary, and the adhesive layer is laminated on the substrate, and the composition for forming a protective film is applied on the release film, and dried if necessary. , and a film for forming a protective film is formed on the release film. Then, the exposed surface of the protective film-forming film is bonded to the exposed surface of the adhesive layer laminated on the substrate, and the protective film-forming film is laminated on the adhesive layer to obtain the above-mentioned laminated sheet.

In addition, when laminating the adhesive layer on the substrate, as described above, instead of applying the adhesive composition on the substrate, the adhesive composition may be applied on a release film and dried if necessary. An adhesive layer is formed on the release film, and the exposed surface of the layer is bonded to one of the surfaces of the substrate to laminate the adhesive layer on the substrate. Regardless of the method, the release film may be removed at any time after formation of the target laminated structure.

According to this, the layers other than the base material constituting the composite sheet for forming a protective film can be laminated by pre-forming the release film and then laminating it on the surface of the target layer. Therefore, the layers that use this step are appropriately selected as needed. , the above-mentioned laminate can be manufactured.

For example, the composite sheet for forming a protective film is usually stored with a release film attached to the surface of the outermost layer (for example, a film for forming a protective film) opposite to the surface facing the support sheet. Therefore, on this release film (preferably, the release-treated surface), a composition for forming a protective film or the like is applied to form a composition constituting the outermost layer, and then dried as necessary to form a composition constituting the outermost layer on the release film. Layer, and then laminate the remaining layers on the exposed surface of the layer opposite to the side in contact with the release film according to any of the above methods, even if the release film is not removed and the bonded state is maintained, the laminated sheet can be obtained.

When the composite sheet for forming a protective film includes the above-mentioned other layers, it is only necessary to appropriately add the step of providing the above-mentioned layers in an appropriate timing of the above-mentioned laminated sheet production step (1) so as to obtain an appropriate arrangement position.

The shape of the laminated sheet produced in the laminated sheet production step (1) is not particularly limited. For example, it is possible to produce a long laminated sheet suitable for winding up in a roll shape, but it is also possible to produce a laminated sheet of other shapes than the long strip.

＜<Preservation steps of laminated sheet＞＞ In the step of storing the above-mentioned laminated sheet, the above-mentioned laminated sheet is stored under pressure in its thickness direction. In this step, the method of storing the above-mentioned laminated sheet in a pressurized state may include, for example: winding the elongated above-mentioned laminated sheet into a roll shape, and keeping the rolled-up laminated sheet in the state of rolling The method in which the generated pressure is applied to one side or both sides of the laminated sheet and preserved; for the laminated sheet that is not rolled into a roll and maintained in an unfolded state, or the above-mentioned sheet that is not long A laminated sheet, a method of storing it with pressure applied to one or both sides thereof, etc.

When winding up the long laminated sheet into a roll shape, it is preferable that the laminated sheet be wound up in the direction of the long side. When winding laminated sheets, for example, the winding tension is preferably 150~170N/m, the winding speed is preferably 45~55m/min, and the taper ratio (reduction rate) of winding tension is preferably 85 ~95%. By employing such winding conditions, the laminated sheet can be stored under more appropriate pressure. This kind of coiling condition is especially suitable for laminates with a thickness of 100-300 μm, a width of 300-500 mm, and a length of 40-60 m, but the size of the laminate is not limited to this.

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

The laminated sheet wound up in the form of a roll can be stored at normal temperature or at room temperature, but it is better to store it in a heated state. By storing under heat and pressure in this way, it is possible to obtain a protective film that is more excellent in laminarity between the adhesive layer and the film for forming a protective film, and the visibility of the protective film or the film for forming a protective film through the support sheet. Use composite sheets.

When winding the laminated sheet into a roll, the heating temperature during storage is not particularly limited, but is preferably 53-75°C, more preferably 55-70°C, and most preferably 57-65°C.

There is no special limit to the storage time when the laminated sheet is rolled into a roll, preferably 24-720 hours (1-30 days), more preferably 48-480 hours (2-20 days), and the best 72~240 hours (3~10 days).

The laminated sheet wound up in the form of a roll can also be processed into a specific shape, such as a film for forming a protective film and a support sheet, and then a plurality of laminates of the film for forming a support sheet and a film for forming a protective film processed in this way can be placed next to it for protection. One side of the film-forming film was bonded to the elongated release film, and the release film was aligned in the longitudinal direction. In this case, the thin film for forming a protective film preferably has the same or almost the same planar shape (usually circular shape) as that of the semiconductor wafer. In addition, the support sheet in this case preferably has the same or almost the same outer peripheral shape as the jig for fixing the support sheet in the cutting device. Also, in this case, it is preferable to provide a belt-shaped sheet near the peripheral edge portion in the short side direction on the laminate bonding surface of the release film so as not to overlap the laminate. This belt-shaped sheet is used to suppress the level difference on the surface of the above-mentioned laminate (also referred to as "lamination mark" in this specification) when the laminate is wound up into a roll. The above-mentioned lamination marks are due to the fact that the lamination position of the above-mentioned laminate (the laminate of the processed support sheet and the film for protective film formation) is not consistent in the radial direction of the reel in the laminate sheet roll, resulting in a high pressure on the surface of the above-mentioned laminate. cause. If the belt-shaped sheet is provided near the peripheral portion, such a high pressure will not be applied to the surface of the layered product, and the occurrence of the layered layer marks will be suppressed.

When the elongated laminated sheet is in an unfolded state instead of being wound in a roll, and when the laminated sheet is not long, it is preferable to store a plurality of these laminated sheets by further lamination. However, when laminating the laminated sheets in this way, it is preferable that the directions of the laminated sheets and the positions of the peripheral portions of the plurality of sheets are aligned with each other.

The shape and size of the non-elongated laminated sheet (in other words, single-piece laminated sheet) are not particularly limited. For example, it is better to use a cutting device to adjust the shape and size of the laminate according to the method suitable for processing a single semiconductor wafer, the shape and size of the semiconductor wafer, and the shape and size of the jig used to fix the support sheet in the cutting device. .

The above-mentioned laminated sheet in a laminated state can be stored at normal temperature or at room temperature, but is preferably stored under heating. By storing under heat and pressure in this way, it is possible to obtain a protective film that is more excellent in laminarity between the adhesive layer and the film for forming a protective film, and the visibility of the protective film or the film for forming a protective film through the support sheet. Use composite sheets. Furthermore, when the laminated sheet is stored under pressure, both the heating temperature and the storage time can be set to be the same as those in the case where the laminated sheet is wound up in a roll shape.

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

In the laminated sheet production step (1) of the production method (S1), the order of lamination (bonding) of the substrate, the adhesive layer, and the protective film forming film is not particularly limited. When laminating the adhesive layer on top of the protective film, prefabricating the film for forming the protective film, and then laminating the film for forming the protective film on the support sheet, either or both of the support sheet and the film for forming the protective film should be laminated before lamination. Separately, pressurized storage was performed in the same manner as in the case of the above-mentioned laminated sheet. By storing the support sheet before lamination under pressure alone, 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 forming a protective film under pressure before lamination, the unevenness of the film for forming a protective film and the surface (second surface) of the protective film facing the adhesive layer (second surface) can be reduced (smoothness increased), To improve the design of protective film forming film and protective film.

That is, the above-mentioned composite sheet for forming a protective film can also be produced, for example, by the following production method (also referred to as "production method (S2)" in this specification) including: The step of laminating the film for forming a protective film on the above-mentioned adhesive layer to produce a laminated sheet formed by laminating layers in the thickness direction of the base material, the adhesive layer, and the film for forming a protective film in this order (also referred to as "laminated sheet production" in this specification) Step (2)"); and the step of storing the above-mentioned laminated sheet under pressure in its thickness direction (preservation step); wherein, before the above-mentioned laminated sheet manufacturing step (2), further comprising: combining the above-mentioned support sheet with A step of applying pressure to one or both of the films for forming a protective film and storing them in the thickness direction (in this specification, the step of storing the support sheet is referred to as the "step of storing the support sheet", and the step of storing the film for forming a protective film It is called "thin film preservation step for protective film formation").

◎Manufacturing method (S2) The above-mentioned manufacturing method (S2) is performed in addition to the above-mentioned laminated sheet manufacturing step (1), which is the implementation of the laminated sheet manufacturing step (2), and additionally implements either or both of the above-mentioned support sheet preservation step and protective film formation film preservation step. Otherwise, it is the same as the above-mentioned manufacturing method (S1).

＜＜Laminate production steps (2)＞＞ The above-mentioned laminated sheet manufacturing step (2), as described above, is similar to the manufacturing method ( The laminated sheet production step (1) of S1) is the same.

＜<Support Sheet Storage Procedure, Protective Film Formation Film Storage Procedure＞＞ The support sheet storage step and the protective film formation film storage step described above are the same as the laminate storage step of the production method (S1), except that the object of preservation is not a laminate but a support sheet or a protective film formation film. carry out. In this case, for example, the storage time of the supporting sheet and the protective film forming film is the same as the case of the laminated sheet, and can be set to 24 to 720 hours (1 to 30 days), 48 to 480 hours (2 to 20 days), and Either of 72 to 240 hours (3 to 10 days).

On the other hand, the step of storing the supporting sheet and the film storing step for forming a protective film are respectively as described above, in addition to changing the storage target, and changing the storage time of the target (support sheet or film for forming a protective film). Except for the changed matters, it was carried out in the same manner as the laminated sheet storage step of the manufacturing method (S1). In this case, for example, the storage time of the supporting sheet and the protective film forming film can be 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 to 10 days). days) any one of them. However, this is only an example of the storage time mentioned above. [Example]

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

＜Raw materials for the production of protective film forming compositions＞ The raw materials used for the production of the composition for forming a protective film are as follows. ・Polymer component (A) (A)-1: an acrylic polymer formed by copolymerization of methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) (weight average molecular weight 370000, glass transition temperature 6°C ) ・Thermosetting components (B1) (B1)-1: Bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184~194g/eq) (B1)-2: Bisphenol A type 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) ・Thermosetting agent (B2) (B2)-1: Dicyandiamide ("ADK HARDENER EH-3636AS" manufactured by ADEKA Corporation, thermally active latent epoxy resin hardener, active hydrogen content 21g/eq) ・Hardening Accelerator (C) (C)-1: 2-phenyl-4,5-dimethylimidazole ("Curezol 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) ・Filler (D) (D)-1: Silica filler ("SC2050MA" manufactured by Admatechs Co., Ltd., a silica filler surface-modified with an epoxy compound, average particle size 0.5 μm) ・Coupling agent (E) (E)-1: 3-Aminopropyltrimethoxysilane ("A-1110" manufactured by NUC Corporation) ・Coloring agent (I) (I)-1: Black pigment (made by Dainichi Seika Co., Ltd.)

[Example 1] ＜Manufacturing of support sheet＞ (Manufacture of Adhesive Composition (I-4)) A non-energy ray-curable adhesive composition (I-4) with a solid content concentration of 30% by mass was produced, which contained an acrylic polymer (100 parts by mass, solid content), and trifunctional diisocyanatoxylylene An ester-based crosslinking agent ("TAKENATE D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)) also contained a mixed solvent of methyl ethyl ketone, toluene, and ethyl acetate as a solvent. The above-mentioned acrylic polymer system is prepared by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass) with a weight average molecular weight of 800000. copolymer.

(manufacturing of support sheet) Use a release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) that has been treated with silicone on one side of a polyethylene terephthalate film, and apply to the release-treated surface. The adhesive composition (I-4) obtained above was heated and dried at 120° C. for 2 minutes to form a non-energy ray curable adhesive layer. At this time, conditions were set so that the thickness of the adhesive layer would be 4 μm, and the adhesive composition (I-4) was applied.

One surface of a polypropylene film (manufactured by Mitsubishi Plastics, thickness 80 μm) is pressed by rotating the uneven surface of a metal roller in a heated state, whereby one surface is uneven and the other surface is smooth (glossy surface) substrate. The maximum height roughness (Rz) was measured in accordance with JIS B 0601:2013 on the uneven surface of this base material, and it was 5 μm.

Next, by bonding the uneven surface of the base material to the exposed surface of the obtained adhesive layer, a support sheet is obtained in which the base material, the adhesive layer, and the release film are laminated in the thickness direction in this order. The width of the obtained support sheet (in other words, the width of the substrate and the adhesive layer) was 400 mm. The supporting sheet of the present invention was obtained as described above.

Next, the evaluation about the unbonded area between the base material and the adhesive layer, which will be described later, was immediately performed on this support sheet. Moreover, this support sheet was used for manufacture of the composite sheet for protective film formation mentioned later, maintaining this state.

＜Manufacture of composite sheet for protective film formation＞ (Manufacture of protective film forming composition (III-1)) Make polymer component (A)-1 (150 mass parts), thermosetting component (B1)-1 (60 mass parts), (B1)-2 (10 mass parts), (B1)-3 (30 mass parts ), (B2)-1 (2 mass parts), hardening accelerator (C)-1 (2 mass parts), filler (D)-1 (320 mass parts), coupling agent (E)-1 (2 mass parts 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 solid concentration of 51% by mass. Composition (III-1) for forming a protective film. In addition, all the blending amounts shown here mean "solid content".

(Manufacture of film for protective film formation) Use a release film (second release film, "SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) that has been released by silicone treatment on one side of a polyethylene terephthalate film, and use it on the release-treated surface The protective film-forming composition (III-1) obtained above was coated with a knife coater, and dried at 100° C. for 2 minutes to obtain a thermosetting protective film-forming film with a thickness of 25 μm.

Furthermore, on the exposed surface of the obtained protective film forming film on the side where the second release film was not provided, a release film (the first release film, "SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) was pasted. The surface is treated to obtain a laminated film in which the first release film is provided on one side of the film for forming a protective film and the second release film is provided on the other side. The width of the obtained laminated film (in other words, the width of the film for protective film formation, the 1st release film, and the 2nd release film) was 400 mm.

(Manufacture of composite sheets for protective film formation) Prepare a set (two pieces) of rollers with a diameter of 5 cm and a region up to a depth of 3 mm from the surface, which is made of heat-resistant polysiloxane rubber with a hardness of 50 degrees. The release film was removed from the adhesive layer of the support sheet obtained above. Also, the first release film was removed from the laminated film obtained above. Then, the exposed surface of the adhesive layer produced by removing the release film and the exposed surface of the film for forming a protective film produced by removing the first release film are opposed to each other, and these support sheets are overlapped with the film for forming a protective film. While forming a laminate, the laminate was passed at a speed of 0.3 m/min through a gap between these rolls set at a temperature of 60° C., and heated and pressed at a pressure of 0.5 MPa (heated lamination). In this way, a laminated sheet having the same laminated structure as the target protective film forming composite sheet (before storage Composite sheet for protective film formation). The width of the obtained laminated sheet (in other words, the width of the support sheet) was 400 mm, and the outer diameter of the film for forming a protective film was 330 mm.

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

Next, the evaluation of the items shown below was performed about the composite sheet for protective film formation of this invention which completed storage under such heating and pressurization conditions.

<Evaluation of support sheet and protective film forming composite sheet> (Measurement of Adhesive Layer Thickness) A test piece having a size of 3 mm×3 mm was cut out from five places of the composite sheet for forming a protective film obtained above. The cutting positions of these five places are one place corresponding to the center in the film for forming a circular protective film, and four places near the peripheral part which are almost point-symmetrical with respect to the center. Among the cutting positions of these 5 places, the distance between the center of 1 place corresponding to the center and the other 4 places near the periphery is 100mm.

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

The newly formed cross sections of these five test pieces were observed using a scanning electron microscope (SEM), and the minimum and maximum values of the thickness of the adhesive layer were determined for each test piece. At this time, the cross-sectional observation area of the test piece is the 1 mm area in the cross-sectional width direction. Then, the average value of these minimum values was adopted as the S value of the adhesive layer, and the average value of these maximum values was adopted as the L value of the adhesive layer. The results are shown in Table 1.

(Evaluation of marking inspection of protective film) Remove the second release film from the protective film forming composite sheet obtained above, and attach the exposed surface (the surface opposite to the adhesive layer side) of the protective film forming film thus produced to an 8-inch semiconductor the backside of the wafer. Attachment at this time was carried out using a film laminating machine ("RAD2700" manufactured by Lintec Corporation). Thereby, the first laminated structure formed by laminating the base material, the adhesive layer, the film for forming a protective film, and the semiconductor wafer in the thickness direction in this order is obtained.

Next, using a laser marking device (“CSM300M” manufactured by EO TECHNICS Co., Ltd.), irradiate the surface (second surface) of the film for forming a protective film in the first laminated structure on the side facing the adhesive layer through the support sheet. Marking is performed by laser light. At this moment, the characters with the size of 0.3mm×0.2mm are printed.

Next, the mark (laser mark) of this film for protective film formation was observed visually through a support sheet, and the visibility of mark (character) was evaluated according to the following reference|standard. The results are shown in Table 1. The marking visibility of the film for forming a protective film evaluated here is considered to be equivalent to that of a protective film. A: The engraving is clear and can be easily inspected. B: The imprint is slightly blurred and cannot be easily seen. C: Marking is not clear and cannot be viewed.

Next, the support sheet (substrate and adhesive layer) is torn off from the film for protective film formation. Then, using an optical microscope (manufactured by KEYENCE Corporation), the line thickness of the inscription (character) formed on the film for protective film formation was measured. As a result, the line thickness was 40 μm or more, and it was clearly marked.

(Evaluation of Adhesion Between Substrate and Adhesive Layer) According to JIS K 5600-5-6, using a rotary cutter (rotary cutter), the 1mm square grid shape of 100 small squares is given to the adhesive layer of the support sheet, and the adhesive tape (cello tape [manufactured by NICHIBAN Co., Ltd.] , registered trademark]), tear off the adhesive tape at an angle of about 60 degrees, 0.5 seconds to 1.0 seconds, and count the number of small squares remaining in the 100 small squares, so as to test the adhesion between the substrate and the adhesive layer. Adhesive evaluation was carried out in accordance with the following judgment criteria. Then, according to the following criteria, the evaluation related to the adhesiveness of a base material and an adhesive layer was performed. The results are shown in Table 1. A: The number of remaining small squares is 90 or more. B: The number of remaining small squares is more than 70 but less than 90. C: The number of remaining small squares is less than 70.

<Manufacture of support sheet and protective film forming composite sheet, and evaluation of support sheet and protective film forming composite sheet> [Example 2] One surface of a polypropylene film (manufactured by Mitsubishi Plastics, thickness 80 μm) is pressed by rotating the uneven surface of a metal roller in a heated state, whereby one surface is uneven and the other surface is smooth (glossy surface) substrate. The unevenness of the uneven surface of the metal roller used at this time was smaller than the unevenness of the uneven surface of the metal roller used in Example 1. The maximum height roughness (Rz) was measured in accordance with JIS B 0601:2013 with respect to the uneven surface of the obtained substrate, and was 1.5 μm.

Except for applying the adhesive composition (I-4) using the substrate obtained above and setting the conditions such that the thickness of the adhesive layer was not 4 μm but 5 μm, a support sheet was produced in the same manner as in Example 1, and Evaluation. Then, except using such a support sheet, the composite sheet for protective film formation was manufactured by the method similar to Example 1, and it evaluated. The results are shown in Table 1.

[Example 3] One surface of a polypropylene film (manufactured by Mitsubishi Plastics, thickness 80 μm) is pressed by rotating the uneven surface of a metal roller in a heated state, whereby one surface is uneven and the other surface is smooth (glossy surface) substrate. The unevenness of the uneven surface of the metal roller used at this time was larger than the unevenness of the uneven surface of the metal roller used in Example 1. The maximum height roughness (Rz) was measured in accordance with JIS B 0601:2013 with respect to the uneven surface of the obtained substrate, and it was 8 μm.

Except for applying the adhesive composition (I-4) using the substrate obtained above and setting the conditions such that the thickness of the adhesive layer was not 4 μm but 10 μm, a support sheet was produced in the same manner as in Example 1, and Evaluation. Then, except using such a support sheet, the composite sheet for protective film formation was manufactured by the method similar to Example 1, and it evaluated. The results are shown in Table 1.

[Comparative example 1] A support was produced in the same manner as in Example 1, except that the adhesive composition (I-4) was applied and the uneven surface of the substrate was not formed under the conditions set so that the thickness of the adhesive layer was not 4 μm but 5 μm. slice, and evaluate. Then, except using such a support sheet, the composite sheet for protective film formation was manufactured by the method similar to Example 1, and it evaluated. The results are shown in Table 1.

[Comparative example 2] A support sheet was produced and evaluated in the same manner as in Example 1 except that the conditions were set so that the thickness of the adhesive layer was not 4 μm but 3 μm, and the adhesive composition (I-4) was applied. Then, except using such a support sheet, the composite sheet for protective film formation was manufactured by the method similar to Example 1, and it evaluated. The results are shown in Table 1.

[Comparative example 3] On one surface of a polypropylene film (manufactured by Mitsubishi Plastics Co., Ltd., thickness 80 μm), pressing is performed by rotating the concave-convex surface of a metal roller in a heated state, whereby one surface is concave-convex and the other surface is smooth. Surface (shiny surface) base material. The unevenness of the uneven surface of the metal roller used at this time is larger than that of the uneven surface of the metal roller used in Example 1. The maximum height roughness (Rz) was measured in accordance with JIS B 0601:2013 with respect to the uneven surface of the obtained base material, and was 14 μm.

Except for applying the adhesive composition (I-4) using the substrate obtained above and setting the conditions such that the thickness of the adhesive layer was not 4 μm but 8 μm, a support sheet was produced in the same manner as in Example 1, and Evaluation. Then, except using such a support sheet, the composite sheet for protective film formation was manufactured by the method similar to Example 1, and it evaluated. The results are shown in Table 1.

[Table 1]

From the above results, it can be seen that for Examples 1-3, the L value/S value of the adhesive layer is above 1.5 (1.5-3.0), and the adhesion between the substrate and the adhesive layer is excellent. Moreover, the L value/S value of the adhesive layer of these Examples is 3.0 or less (1.5-3.0), and the marking visibility of a protective film (thin film for protective film formation) is excellent.

On the other hand, the L value/S value of the adhesive layer of Comparative Example 1 was 1.0, and the adhesiveness between the base material and the adhesive layer was poor. Therefore, there is a situation of peeling between the substrate and the adhesive layer.

In addition, the L value/S value of the adhesive layer of Comparative Examples 2 and 3 was 5.0 and 7.0, respectively, and the marking visibility of the protective film (thin film for protective film formation) via the support sheet was poor.

Furthermore, the S value of the adhesive layer of Examples 1-3 is 2 μm or more (2-7 μm), although the data is not particularly shown, but the lamination property between the adhesive layer and the film for forming a protective film is excellent. Moreover, the L value of the adhesive layer of these Examples is 8 micrometers or less (2-7 micrometers), and the marking visibility of a protective film (thin film for protective film formation) is more excellent.

In addition, in Examples 1 to 3, there is no unbonded area between the base material and the adhesive layer, and between the adhesive layer and the film for forming a protective film, or even if there is, the distance between layers is small, and the area for forming a protective film is small. The composite sheet has good properties. Furthermore, in Examples 1 to 3, the unevenness of the second surface of the protective film-forming film was small, the appearance of the protective film-forming film was excellent, and a protective film with high designability could be formed. (industrial availability)

The present invention is applicable to the manufacture of semiconductor devices.

1A, 1B, 1C‧‧‧Composite sheet for protective film formation 10‧‧‧Support sheet 10a‧‧‧Support sheet facing the protective film forming film side (first surface) 10b‧‧‧Support sheet facing protective film formation The surface on the opposite side to the film side (second surface) 11‧‧‧substrate 11a‧‧‧the surface of the substrate on the side facing the adhesive layer (first surface, concave-convex surface) 11b‧‧‧substrate facing the adhesive layer The surface on the opposite side (the second surface) 12‧‧‧adhesive layer 12a‧‧‧the surface (first surface) on the opposite side of the adhesive layer facing the substrate side 12b‧‧‧adhesive layer facing the substrate side Surface (second surface) 13, 23‧‧‧film for forming protective film 13a‧‧‧surface (first surface) on the opposite side of the film for forming protective film facing the adhesive layer side (first surface) 13b‧‧‧for forming protective film The surface of the film on the side facing the adhesive layer (second surface) 15‧‧‧peeling film 16‧‧‧adhesive layer for jigs 16a‧‧‧the adhesive layer for jigs is not in contact with the side 23b‧‧ of the film for forming a protective film _‧The surface of the protective film forming film facing the adhesive layer (the second _surface ) _91,92 ‧‧‧Maximum thickness of adhesive layer

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

1A‧‧‧Composite sheet for protective film formation

10‧‧‧Support piece

10a‧‧‧Support sheet facing the protective film forming film side (first surface)

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

11‧‧‧Substrate

11a‧‧‧The surface of the substrate on the side facing the adhesive layer (the first surface, concave-convex surface)

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

12‧‧‧adhesive layer

12a‧‧‧Adhesive layer on the side opposite to the base material side (first side)

12b‧‧‧The surface of the adhesive layer facing the substrate side (second surface)

13‧‧‧Film for protective film formation

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

13b‧‧‧The surface of the protective film forming film facing the adhesive layer (second surface)

15‧‧‧Peeling film

16‧‧‧Adhesive layer for jigs

16a‧‧‧The adhesive layer for jigs is not in contact with the surface of the protective film forming film

Claims (4)

A composite sheet for forming a protective film, which is attached to an adhesive layer in a support sheet and provided with a thin film for forming a protective film. The above-mentioned support sheet includes a base material, and a The above-mentioned adhesive layer, wherein, the surface of the above-mentioned base material facing the above-mentioned adhesive layer is a concave-convex surface; test pieces are cut from 5 places of the above-mentioned support sheet, and the minimum thickness of the adhesive layer is calculated for these 5 test pieces. In the case of the maximum value and the maximum value, the ratio (L value/S value) of the average value (L value) of the above-mentioned maximum value to the average value (S value) of the above-mentioned minimum value is 1.2 or more and less than 5.0. The composite sheet for forming a protective film as claimed in claim 1, wherein the adhesive layer is in direct contact with the concave-convex surface of the substrate. For example, the composite sheet for forming a protective film in claim 1 or 2, wherein the light transmittance of the support sheet at a wavelength of 532nm or a wavelength of 1064nm is 30% or more. A method of manufacturing a semiconductor device with a protective film, which is a method of manufacturing a semiconductor device with a protective film using the composite sheet for forming a protective film according to any one of claims 1 to 3 of the patent application, comprising the following steps: (1) A step of producing a first laminated structure formed by laminating a base material, an adhesive layer, a film for forming a protective film, and a semiconductor wafer in the thickness direction in this order, and (2) by forming the first laminated structure The process of irradiating the surface of the adhesive layer side of the protective film forming film in the body with laser light through the support sheet to perform marking.

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