TW202001985A - Supporting sheet and composite sheet for forming protective film - Google Patents

Abstract

A supporting sheet of the present embodiment includes a substrate and an adhesive layer on the substrate, wherein the surface of the adhesive layer side of the substrate is an uneven surface. When 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 five adhesive layers are measured, the average minimum thickness is 1.5 [mu]m or more and the average maximum thickness is 9 [mu]m or less. A composite sheet for forming a protective film of the present embodiment includes the supporting sheet, and also includes a film for forming the protective film on the adhesive layer in the supporting sheet.

Description

Composite sheet for forming support sheet and protective film

The invention relates to a composite sheet for forming a support sheet and a protective film. This application claims priority based on PCT/JP2018/013636 filed on March 30, 2018, and the contents are used here.

In recent years, manufacturing of semiconductor devices to which the so-called face-down packaging method is applied has been carried out. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on the circuit surface may be used to bond the electrodes to the substrate. Therefore, the back surface of the semiconductor wafer opposite to the circuit surface may be exposed.

On the back surface of the semiconductor wafer exposed here, a resin film containing an organic material is formed as a protective film and incorporated into the semiconductor device as a semiconductor wafer with a protective film. The protective film is used to prevent cracks on the semiconductor wafer after the dicing step, packaging, and the like.

Such a protective film is formed, for example, by hardening a protective film forming film having curability. In addition, the non-curing protective film forming film whose physical properties are adjusted may be directly used as a protective film. Then, the protective film forming film is attached to the back surface of the semiconductor wafer and used. The film for forming a protective film, for example, will be integrated with the support sheet used in the processing of a semiconductor wafer, and will be attached to the back surface of the semiconductor wafer in the state of a composite film for forming a protective film; The integrated state of the wafer is attached to the back of the semiconductor wafer.

After the protective film forming composite sheet is attached to the back surface of the semiconductor wafer with the protective film forming film thereon, the protective film forming layer is appropriately formed and protected at appropriate timings by hardening the protective film forming film. Cutting of the film for film formation or the protective film, singulation (dicing) of the semiconductor wafer of the semiconductor wafer, and picking up the semiconductor wafer provided with the film for protective film formation or the protective film after cutting on the back surface (with protective film) (A semiconductor wafer for forming a film or a semiconductor wafer with a protective film), etc. Then, when picking up a semiconductor wafer with a film for forming a protective film, the semiconductor film with a protective film is formed by curing the film for forming a protective film, and finally a semiconductor wafer with a protective film is used to manufacture a semiconductor device. In this way, the support sheet in the composite sheet for forming a protective film can be used as a dicing sheet. In addition, when the film for forming a protective film is non-curable, in each of these steps, the film for forming a protective film is operated as it is as a protective film.

On the other hand, after the protective film forming film is not integrated with the support sheet and is attached to the back surface of the semiconductor wafer, the exposed surface of the protective film forming film opposite to the attachment surface of the semiconductor wafer , Attached to the support sheet. Thereafter, a semiconductor wafer with a protective film or a semiconductor wafer with a protective film-forming film is obtained in the same manner as in the case of using the composite film for forming a protective film, and a semiconductor device is manufactured. At this time, although the protective film forming film is attached to the back surface of the semiconductor wafer in a state where it is not integrated with the support sheet, the protective film is formed by integration with the support sheet after attachment Composite sheet.

As such a composite sheet for forming a protective film, for example, there is disclosed a dicing tape-integrated film for semiconductor back surface protection (a composite sheet for forming a protective film), comprising: a base material having an uneven surface and the above-mentioned uneven processing on the base material A dicing tape (support sheet) having an adhesive layer is laminated on the face side, and a film for protecting the back surface of the semiconductor (film for forming a protective film) is laminated on the adhesive layer of the dicing tape, and the haze value of the dicing tape is 45 % Or less dicing tape integrated semiconductor backside protection film (refer to Patent Document 1).

However, in the composite sheet for forming a protective film (a dicing tape-integrated semiconductor back surface protection film) disclosed in Patent Document 1, since the adhesive layer is deposited on the uneven processing surface side of the base material, the adhesive layer The film for protective film formation (film for semiconductor back surface protection) and the like on this adhesive layer show the influence of the above-mentioned irregularities. For example, since the surface of the adhesive layer on the side of the protective film forming film becomes a concave-convex surface, an area where the adhesive layer and the protective film forming film are not bonded between the adhesive layer and the protective film forming film (non-sticking) Area) to reduce the stackability of the adhesive layer and the protective film forming film. In addition, on the surface of the protective film or the film for forming a protective film on the adhesive layer side, printing may be performed by laser irradiation, but the thickness of the adhesive layer is not uniform and the adhesive layer is thick, sometimes separated The visibility of the printing on the substrate and adhesive layer is reduced. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 5432853

[Problems to be solved by the invention]

An object of the present invention is to provide a support sheet and a composite sheet for forming a protective film including the above support sheet. The support sheet is formed by including an adhesive layer on the concave-convex surface side of the base material, wherein the adhesive layer includes a protective film forming layer In the composite sheet for forming a protective film of a film, good stackability between the adhesive layer and the film for forming a protective film can be achieved, and good legibility of the support sheet through the protective film or the film for forming a protective film can be achieved. [Means for solving the problem]

The invention provides a support sheet comprising a base material and an adhesive layer on the base material. The surface of the base material on the side of the adhesive layer is a concave-convex surface and is cut out from 5 places of the support sheet For the test piece, among the five test pieces, when the minimum and maximum thicknesses of the respective adhesive layers were obtained, the average value of the minimum value was 1.5 μm or more, and the average value of the maximum value was 9 μm or less.

In the support sheet of the present invention, the adhesive layer may directly contact the uneven surface of the base material. In addition, the present invention provides a composite sheet for forming a protective film, which includes a film for forming a protective film on the adhesive layer in the support sheet. [Effect of invention]

By using the supporting sheet of the present invention to form a composite sheet for forming a protective film, good stackability between the adhesive layer and the film for forming a protective film can be achieved, and good printing of the supporting sheet through the protective film or the film for forming a protective film can be achieved Recognition.

◇Composite sheet for forming support sheet and protective film A support sheet according to an embodiment of the present invention is a support sheet including a base material and an adhesive layer on the base material. The surface of the base material on the adhesive layer side is a concave-convex surface, cut from 5 places on the support sheet Test piece, out of the five test pieces, the minimum and maximum values of the thickness of each adhesive layer, the average value of the above minimum (in this specification, sometimes referred to as "S value" ) Is 1.5 μm or more, and the average value of the maximum value (sometimes referred to as “L value” in this specification) is 9 μm or less. In addition, the composite sheet for forming a protective film according to an embodiment of the present invention includes the film for forming a protective film on the adhesive layer in the support sheet.

The support sheet includes an adhesive layer on the uneven surface side of the base material. In the composite sheet for forming a protective film including the support sheet, the influence of the uneven surface is suppressed. More specifically, when the S value of the adhesive layer is 1.5 μm or more, the stackability between the adhesive layer and the film for forming a protective film becomes good. In this specification, "lamination", unless otherwise specified, refers to the normality of the lamination state of the target two layers. "Good lamination" means, for example, that there are no non-bonding regions (voids) between the two adjacent layers, or the number of non-bonding regions is small and the distance between the non-bonding regions is small. On the other hand, when the L value of the adhesive layer is 9 μm or less, the legibility of the support sheet through the protective film or the protective film forming film becomes good

The above-mentioned test piece was cut out from 5 places of the support sheet, and the support sheet was cut in the entire area in the thickness direction to obtain the test sheet. The test piece is a small piece including all layers constituting the support sheet.

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

The planar shape of the test piece, that is, the shape of the accumulated surface or exposed surface of each layer (base material, adhesive layer, etc.) constituting the test piece is preferably a polygon, and from the viewpoint of ease of cutting out the test piece, a quadrilateral For better.

Examples of preferred test pieces include, for example, those having a laminate surface or exposed surface of each layer (base material, adhesive layer, etc.) constituting the test piece, and having a size of 3 mm×3 mm. However, these are only examples of better test pieces.

The cutting position of the test piece in the support sheet at 5 places is not particularly limited, but in order to obtain the S value and L value of the adhesive layer with higher accuracy, it may be considered to select the following deposition plan of the protective film forming film position. For example, among the predetermined positions for lamination of one protective film forming film in the support sheet, 5 are listed, in which the center (center of gravity) of the protective film forming film is one of the predetermined positions, and the protective film The portion of the film for formation that is close to the edge portion and almost point-symmetrical with respect to the center (center of gravity) portion is the predetermined four positions.

In the support sheet, the distance between the center (center of gravity) of the cut-out position of the test piece is preferably 50 to 200 mm. In this way, the S value and the L value of the adhesive layer can be obtained with higher accuracy.

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

In the test piece, the profile can be formed by a conventional method. For example, by using a conventional cross-section sampler (Cross section polisher), deviation can be suppressed and a cross-section can be formed on the test piece with high reproducibility.

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

In the above-mentioned cross section of each test piece, the minimum and maximum thickness regions of the adhesive layer are measured so as to be at a right angle (approximately) to the stacking direction of each layer (base material, adhesive layer, etc.) constituting the test piece. It is preferably a region of 50 to 1500 μm with respect to the accumulation surface or exposed surface of each layer). In this way, the minimum and maximum thickness of the adhesive layer can be measured with high efficiency and high accuracy.

When the minimum value of the thickness of the adhesive layer is compared between the support sheet that does not constitute the composite sheet for forming a protective film and the support sheet constituting the composite sheet for forming a protective film, these minimum values are the same as each other, or constitute a protective film The above-mentioned minimum value of the support sheet of the composite sheet for forming is a slightly small degree, and in this small case, the difference between the two is negligible. The maximum value of the thickness of the adhesive layer is also the same. That is, when the maximum value of the thickness of the adhesive layer is compared between the support sheet that does not constitute the composite sheet for forming a protective film and the support sheet constituting the composite sheet for forming a protective film, these 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 smaller. In such a small case, the difference between the two is negligible. Therefore, the test piece cut out from the composite film for protective film formation may be used instead of the support piece, and the same method as when the test piece cut out from the support piece may be used to obtain the S value and the L value of the adhesive layer. When the test piece cut out from the composite film for protective film formation is used in this manner, when the S value of the adhesive layer is 1.5 μm or more and the L value of the adhesive layer is 9 μm or less, the composite film for protective film formation reflects the above Invent the effect.

That is, the composite sheet for forming a protective film according to an embodiment of the present invention is a composite sheet for forming a protective film including a film for forming a protective film on the adhesive layer in the support sheet, and from the composite sheet for forming the protective film Test pieces were cut out at 5 places, and the minimum and maximum values of the thickness of each adhesive layer were obtained from these 5 test pieces, and the average value (S value) of the minimum value was 1.5 μm or more. The average value (L value) of the maximum value is 9 μm or less.

The test piece cut out from the protective film forming composite sheet is obtained by cutting the entire protective film forming composite sheet in its thickness direction, and is a small piece including all layers constituting the protective film forming composite sheet .

Hereinafter, the overall configuration of the composite sheet for forming a protective film of the present invention will be described with reference to the drawings. In addition, the drawings used in the following description are for easy understanding of the characteristics of the present invention. For convenience, the main part may be enlarged and the size ratio of each component may not be the same as the actual one.

1 is a cross-sectional view schematically showing a composite sheet for forming a support sheet and a protective film according to an embodiment of the present invention. The composite sheet 1A for forming a protective film shown here includes a base material 11, an adhesive layer 12 on the base material 11, and a film 13 for forming a protective film on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, in other words, the protective film forming composite sheet 1A includes a surface on the support sheet 10 side (in this specification, it is sometimes referred to as a "first surface") 10a. The structure of the film 13 for forming a protective film is laminated on top. Moreover, the composite sheet 1A for protective film formation further includes the peeling film 15 on the film 13 for protective film formation.

In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one side of the base material 11 (sometimes referred to as a "first surface" in this specification) 11a, and the adhesive layer 12 is on the side of the base material 11 The opposite side surface (in this specification, it is sometimes referred to as the "first surface") 12a of the full-area layer protective film forming film 12a, the surface on the side opposite to the adhesive layer 12 side of the protective film forming film 13 ( In this specification, it is sometimes referred to as the "first surface") part of 13a, that is, the adhesive layer 16 for the jig is deposited in the area near the peripheral edge portion, in the first surface 13a of the protective film forming film 13 The surface of the adhesive layer 16 for the jig and the surface 16a (upper surface and side surface) of the adhesive layer 16 for the jig not contacting the protective film forming film 13 are not laminated, and the peeling film 15 is laminated. In addition, in FIG. 1, the symbol 13b indicates a surface on the adhesive layer 12 side of the protective film forming film 13 (in this specification, it is sometimes referred to as a "second surface").

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

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

In the composite sheet 1A for forming a protective film, the surface of the base material 11 on the side opposite to the adhesive layer 12 side (in this specification, it is sometimes referred to as "second surface") 11b may be an uneven surface and a smooth surface (not (Rough surface, smooth surface), but smooth surface is preferred. The second surface 11b of the base material 11 may also be referred to as the surface of the support sheet 10 on the side opposite to the protective film forming film 13 side (in this specification, it is sometimes referred to as a "second surface") 10b. The "concave surface" and "smooth surface" will be described in detail later.

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

2 is a cross-sectional view schematically showing a composite sheet for forming a protective film and a supporting sheet according to another embodiment of the present invention. In the subsequent figures of FIG. 2, the same constituent elements as those shown in the already described figures are denoted by the same symbols as in the already explained figures, and their detailed descriptions are omitted.

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

In the composite sheet 1B for forming a protective film, the first surface 11a of the base material 11 is also an uneven surface. In addition, the adhesive layer 12 is provided to directly contact the first surface (concavo-convex surface) 11a of the base material 11. Therefore, the surface (second surface) 12b on the base material 11 side of the adhesive layer 12 is an uneven surface. In the composite sheet 1B for forming a protective film, the second surface 11b of the base material 11 (in other words, the second surface 10b of the support sheet 10) may be any one of an uneven surface and a smooth surface (non-concavo-convex surface). Face is better.

In the composite sheet 1B for forming a protective film shown in FIG. 2, in a state where the peeling film 15 is removed, a semiconductor wafer is attached to a part of the center side of the first surface 13 a of the film for forming a protective film 13 ( The back surface of (omitted in the figure), and the area near the peripheral portion is attached to a jig such as a ring frame and used.

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

In the composite sheet 1C for forming a protective film, the adhesive layer 12 is deposited on the first surface 11 a of the base material 11, and a part of the first surface 12 a of the adhesive layer 12 is formed, that is, a protective film is formed on the central side region.用膜23。 With membrane 23. Then, on the first surface 12a of the adhesive layer 12, the area 23 where the protective film forming film 23 is not laminated and the surface 23a (upper and side surfaces) of the protective film forming film 23 not contacting the adhesive layer 12 are laminated Peeling film 15. In addition, in FIG. 3, the symbol 23b represents the surface of the protective film forming film 23 on the side of the adhesive layer 12 (in this specification, it is sometimes referred to as a "second surface").

The protective film forming composite sheet 1C has a surface area smaller than the surface area of the adhesive layer 12 when viewed from above in a plan view, and has a shape such as a circle.

In the composite sheet 1C for forming a protective film, the first surface 11a of the base material 11 is an uneven surface. In addition, the adhesive layer 12 is provided to directly contact the first surface (concavo-convex surface) 11a of the base material 11. Therefore, the surface (second surface) 12b on the base material 11 side of the adhesive layer 12 is an uneven surface. In the composite sheet 1C for forming a protective film, the second surface 11b of the base material 11 (in other words, the second surface 10b of the support sheet 10) may be any one of an uneven surface and a smooth surface (non-concavo-convex surface). Smooth surface is better.

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

In addition, in the composite sheet 1C for forming a protective film shown in FIG. 3, the first surface 12a of the adhesive layer 12 may also be deposited in the area where the protective film forming film 23 is not laminated. Adhesive layer for jig (not shown). The composite sheet 1C for forming a protective film including such an adhesive layer for a jig is the same as the composite sheet for forming a protective film shown in FIG. 1, and the upper surface of the adhesive layer for a jig is attached to a jig such as a ring frame And use.

As described above, the composite sheet for forming a protective film may include an adhesive layer for jigs regardless of the form of the support sheet and the film for forming a protective film. However, in general, as shown in FIG. 1, as the composite film for forming a protective film including an adhesive layer for a jig, it is preferable to include an adhesive layer for a jig on the film for forming a protective film.

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

For example, in the composite sheet for forming a protective film as shown in FIGS. 1 to 3, an intermediate layer may be provided between the base material 11 and the adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by stacking the substrate, the intermediate layer, and the adhesive layer in the thickness direction. As the intermediate layer, an arbitrary intermediate layer can be selected according to the purpose. In addition, as shown in FIGS. 1 to 3, the composite sheet for forming a protective film may be provided with a layer other than the intermediate layer at any place. In addition, in the composite sheet for forming a protective film, a gap may be formed between the release film and the layer directly in contact with the release film. In addition, in the composite sheet for forming a protective film, the size, shape, etc. of each layer can be arbitrarily adjusted according to the purpose.

However, as shown in FIGS. 1 to 3, in the composite sheet for forming a protective film, it is better to directly contact the uneven surface (first surface) of the substrate with the adhesive layer; in other words, between the substrate and the adhesive layer Without an intermediate layer, it is preferable to directly contact the adhesive layer on the base material and laminate. In addition, in the composite film for forming a protective film, it is preferable that the film for forming the protective film directly contacts the first surface of the adhesive layer; in other words, the adhesive is not provided with another layer between the adhesive layer and the film for forming the protective film. It is preferable that the layer is in direct contact with the film for forming a protective film, and the layer is stacked. Then, in the composite sheet for forming a protective film, it is better to satisfy the above conditions at the same time, that is, to directly contact each other in the thickness direction of the substrate, the adhesive layer, and the film for forming a protective film in this order. The buildup of the layer is better.

The support sheet is preferably transparent. The support sheet can also be colored according to the purpose, and other layers can also be evaporated. For example, when the film for forming a protective film is energy ray curable, the support sheet is preferably one that can penetrate energy ray.

In this specification, "energy rays" refer to those having energy quanta in electromagnetic waves or charged particle beams, and examples thereof include ultraviolet rays, radiation, and electron beams. Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, fusion lamp, xenon lamp, black light, or LED lamp as a source of ultraviolet rays. The electron beam can be irradiated by an electron beam accelerator or the like. In this specification, "energy ray hardenability" refers to the property of being hardened by irradiating energy rays, and "non-energy ray hardening property" refers to the property of not being hardened even when irradiated with energy rays.

In the support sheet, the transmittance of light with a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the above-mentioned light transmittance in these ranges, when the protective film forming film is irradiated with energy rays (ultraviolet rays) through the support sheet, the degree of curing of the protective film forming film is further improved. In the support sheet, the upper limit of the transmittance of light with a wavelength of 375 nm is not particularly limited. For example, the above-mentioned light transmittance may be 95% or less.

In the support sheet, the transmittance of light with a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the above-mentioned light transmittance in these ranges, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and when printing on it, the characters can be printed more clearly. In the support sheet, the upper limit of the transmittance of light with a wavelength of 532 nm is not particularly limited. For example, the above-mentioned light transmittance may be 95% or less.

In the support sheet, the transmittance of light with a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the above-mentioned light transmittance in these ranges, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and when printing on it, the characters can be printed more clearly. In the support sheet, the upper limit of the transmittance of light with a wavelength of 1064 nm is not particularly limited. For example, the above-mentioned light transmittance may be 95% or less.

The penetration clarity of the support sheet is preferably 30 or more, more preferably 100 or more, and particularly preferably 200 or more. With the above-mentioned penetration sharpness in this range, it is easier to confirm the floating peeling of the protective film forming film, unsuitable printing and defects, etc. via the support sheet. The penetration clarity of the support sheet is not particularly limited. For example, the above-mentioned penetration sharpness may be 430 or less. The penetration clarity of the support sheet was measured according to JIS K 7374-2007.

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

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

In this specification, the "concavo-convex surface" refers to a surface that has a maximum height roughness Rz of 0.01 μm or more as prescribed by JIS B 0601:2013. In addition, "smooth surface" refers to a surface that is not uneven and has high smoothness, and is also called "non-concave surface" or "smooth surface". For example, the smooth surface also includes a surface with extremely small unevenness that does not reach the above-mentioned uneven surface.

In the base material, only one surface may be an uneven surface, or both surfaces may be an uneven surface, but it is preferable that only one surface is an uneven surface. In other words, in the above-mentioned base material, it is preferable that only one surface is a smooth surface. In the support sheet, the uneven surface of the base material becomes the surface including the adhesive layer side.

The base material may be composed of one layer (single layer), or composed of more than two plural layers, and when composed of plural layers, these plural layers may be the same as or different from each other, etc. The combination of plural layers is not particularly limited. When the base material is composed of a plurality of layers, the outermost surface (the surface closest to the adhesive layer or the two surfaces closest to and farthest from the adhesive layer) of the plurality of layers becomes the above-mentioned uneven surface .

In this specification, it is not limited to the case of a substrate, and "a plurality of layers may be the same or different from each other", meaning "all layers may be the same, all layers may be different, or only a part of the layers may be the same" In addition, "the plural layers are different from each other" means "at least one of the constituent materials and the thickness of each layer is different."

In the uneven surface (first surface) of the side of the substrate including the adhesive layer, the maximum height roughness (Rz) measured according to JIS B 0601:2013 is preferably 0.01 to 8 μm, preferably 0.1 to 7 μm For better, 0.5~6μm is especially good. When the Rz of the base material is equal to or higher than the lower limit value, the base material is individually wound into a roll shape, and the occurrence of unsmoothness during unwinding can be suppressed. In addition, in the manufacturing process of the support sheet or the composite sheet for forming a protective film, the layered product including the base material can similarly prevent the occurrence of irregularities during winding and unwinding. On the other hand, when the Rz of the base material is equal to or less than the upper limit, the lamination of the adhesive layer and the film for forming a protective film, and the legibility of the protective film or the film for forming a protective film through the support sheet are both Become good.

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

As a constituent material of the above-mentioned base material, for example, various resins may be mentioned. Examples of the resins include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, and polybutadiene Polyolefins other than polyethylene such as polymethylpentene and norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene -Vinyl copolymers such as norbornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as a monomer) ); Polystyrene; Polycycloolefin; Polyethylene terephthalate, Polyethylene naphthalate, Polybutylene terephthalate, Poly(ethylene isophthalate) ), polyethylene-2,6-naphthalene dicarboxylate, all structural units are polyesters such as fully aromatic polyesters having aromatic ring groups; copolymers of two or more of the above polyesters; poly( Meth)acrylate; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polysulfide benzene; polysulfone; polyetherketone, etc. In addition, as the above-mentioned resin, for example, a polymer alloy (polymer alloy) such as a mixture of the above-mentioned polyester and other resins may be mentioned. The polymer blend of the above-mentioned polyester and resins other than that is preferably a smaller amount of resins other than polyester. In addition, as the above-mentioned resin, for example, a cross-linked resin in which one or more of the above-mentioned resins exemplified above are cross-linked; and one or more of the above-mentioned resins exemplified above are used. Modified resins such as ionic polymers.

In this specification, "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same meaning applies to terms similar to (meth)acrylic acid, for example, "(meth)acryloyl" is a concept that includes both "acryloyl" and "methacryloyl", "(meth ") Acrylate" is a concept that includes both "acrylate" and "methacrylate".

The resin constituting the base material may be only one kind, or two or more kinds, and if there are two or more kinds, the combination and ratio may be arbitrarily selected.

The thickness of the substrate is preferably in the range of 50 to 300 μm, and more preferably in the range of 60 to 150 μm. When the thickness of the base material is within such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer are further improved. Since the base material has an uneven surface as described above, its thickness varies depending on the position of the base material. Therefore, the minimum value of the thickness of the base material may be equal to or greater than the above lower limit value, and the maximum value of the thickness of the base material may be equal to or less than the upper limit value. In addition, the "thickness of the substrate" refers to the thickness of the entire substrate, for example, the thickness of the substrate composed of a plurality of layers refers to the total thickness of all the layers constituting the substrate.

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

For example, according to the method described previously, a test piece is cut out from a plurality of places (for example, 5 places) of a composite sheet for forming a support sheet or a protective film, and in this test piece, the minimum and maximum thickness of the base material is obtained When the average value of the minimum value and the maximum value are further obtained from these values, the average value of the minimum value may be equal to or greater than the lower limit of the thickness of the substrate, and the average value of the maximum value may be The upper limit of the thickness of the base material is equal to or less than.

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

The substrate is preferably transparent. The base material can be colored according to the purpose, and other layers can also be evaporated. For example, when the film for forming a protective film is energy ray curable, the substrate is preferably one that can penetrate energy ray.

In order to improve the adhesion between the substrate and the layer directly in contact with the adhesive layer provided thereon, corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment may be performed on the surface , Flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments. In addition, the base material may be a primer applied to the surface. In addition, the substrate may also have an antistatic coating; when the composite film for forming a protective film is laminated and stored, the substrate is prevented from adhering to other sheets, the substrate is prevented from being attached to the layer of the vacuum table, etc.

The substrate can be manufactured by a conventional method. For example, a resin-containing substrate can be produced by molding a resin composition containing the above resin.

When a base material having no uneven surface (in other words, a base material having smooth surfaces on both sides) is used, the smooth surface of the base material may be uneven. The roughening process can be performed by a conventional method. For example, by using a metal roller or a metal plate having an uneven surface, and pressing the above uneven surface onto the smooth surface of the base material, the smooth surface of the base material can be unevenly processed. At this time, it is preferable that the heated metal roller or metal plate is pressed against the smooth surface of the base material. In addition, the smooth surface of the base material may also be roughened by sandblasting or solvent treatment.

○Adhesive layer The adhesive layer is in the form of a sheet or a film. In the adhesive layer, generally, regardless of whether there is an intermediate layer between the base material and the adhesive layer, it is still affected by the above-mentioned uneven surface of the base material, and at least the surface on the base material side is an uneven surface.

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

Here, the base material and the adhesive layer will be described in detail while referring to the drawings. 4 is an enlarged cross-sectional view illustrating a composite sheet for forming a protective film according to an embodiment of the present invention. Here, the composite sheet 1A for forming a protective film shown in FIG. 1 will be described as an example. In addition, in FIG. 4, illustration of the release film is omitted.

As previously described, the first surface 11a of the base material 11 is a concave-convex surface. Then, the adhesive layer 12 is provided to directly contact the first surface (concavo-convex surface) 11 a of the base material 11, and the second surface 12 b of the adhesive layer 12 becomes easy to adhere to the first surface 11 a of the base material 11. Therefore, the second surface 12b of the adhesive layer 12 is also an uneven surface.

Adhesive layer thickness T _a 12 is not necessarily a constant value, depending on the portion of adhesive layer 12 varies. Here, the minimum value of the thickness of the adhesive layer 12 is represented by the symbol T _a1 , and the maximum value of the thickness of the adhesive layer 12 is represented by the symbol T _a2 .

In the composite sheet 1A for forming a protective film, test pieces were cut out from 5 of them, and a cross section was formed among these 5 test pieces. In this newly formed section, the minimum thickness of the individual adhesive layer was obtained The value T _a1 and the maximum value T _a2 . Then, from at least 5 T _a1 , the average value (the above S value) is 1.5 μm or more; from at least 5 T _a2 values, the average value (the above L value) is 9 μm or less.

A test piece was cut out from the composite sheet for protective film formation 1A, a cross-section was formed on the test piece, and the minimum value T _a1 and the maximum value T _a2 of the thickness of the adhesive layer on the above-mentioned cross-section were measured. The test piece was cut out in the same way as the support sheet of the composite sheet for film formation.

In addition, the enlarged cross-sectional view of the support sheet that does not constitute the composite sheet for forming a protective film is the same as that in FIG. 4 in which the film 13 for forming the protective film is omitted.

The composite sheet 1A for forming a protective film means that there is a region where the substrate 1 and the adhesive layer 12 are not bonded between the substrate 1 and the adhesive layer 12 (in this specification, it is sometimes called "Non-fitting area" 91. However, even if the protective film forming composite sheet 1A has such a non-lamination area 91, the size of the non-lamination area 91 in the thickness direction of the protective film forming composite sheet 1A is, for example, 0.5 μm or less. 1A can be said to have good stackability between the base material 11 and the adhesive layer 12 and has good characteristics.

In addition, in this specification, "the size of the non-lamination area in the thickness direction of the composite sheet for protective film formation" means "the thickness direction of the sheet in the two adjacent layers in the composite sheet for protective film formation" "Interlayer distance above" is sometimes simply referred to as "interlayer distance". For example, the above “the size of the non-lamination area 91 in the thickness direction of the protective film forming composite sheet 1A” means “between the base material 11 and the adhesive layer 12 in the thickness direction of the sheet 1A” Interlayer distance." When the size (interlayer distance) of the non-laminated region at one location changes, the maximum value is adopted as the size (interlayer distance) of the non-laminated region.

The size (interlayer distance) of the non-laminated area can be measured by the same method as in the case of the thickness of the adhesive layer described above, for example. That is, a cross-section can be formed on the test piece of the composite film for forming a protective film by the same method as when obtaining the thickness of the adhesive layer, and at this cross-section, the size of the non-bonding region can be obtained. Alternatively, a test piece may not be prepared, and a cross-section may be formed on the composite film for forming a protective film. At this cross-section, the size of the non-lamination area may be obtained.

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

In the composite sheet 1A for forming a protective film, the non-lamination area 91 may not exist at all.

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

If the S value of the adhesive layer is 1.5 μm or more and less than 9 μm, it is not particularly limited, but it is preferably 1.7 μm or more, more preferably 1.9 μm or more, for example, it may be 2.3 μm or more, 2.7 μm or more, 3.1 Any one of μm or more and 3.5 μm or more. When the S value is equal to or higher than the lower limit value, the lamination property between the adhesive layer and the film for forming a protective film becomes better.

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

The S value of the adhesive layer can be arbitrarily adjusted within a set range by arbitrarily combining the above-described preferred lower limit value and upper limit value. For example, the S value of the adhesive layer is preferably from 1.5 to 8 μm, more preferably from 1.7 to 8 μm, and even more preferably from 1.9 to 8 μm, for example, it can be 2.3 to 8 μm, 2.7 to 8 μm, 3.1 to 8 μm, and 3.5 Any of ~8μm. However, these are examples of the S value of the adhesive layer.

The L value of the adhesive layer is not particularly limited as long as it is 9 μm or less and more than 1.5 μm, but it is preferably 8.6 μm or less, more preferably 8.3 μm or less, for example, 7.7 μm or less, 7.3 μm or less, 6.9 Any one of less than μm and less than 6.5 μm. When the L value is equal to or lower than the upper limit value, the legibility of the protective film or the protective film forming film through the support sheet becomes better.

On the other hand, the L value of the adhesive layer may be 2.5 μm or more, for example. Such an adhesive layer becomes easier to form.

The L value of the adhesive layer can be appropriately adjusted within a set range by arbitrarily combining the above-described preferred lower limit value and upper limit value. For example, the L value of the adhesive layer is preferably 2.5 to 9 μm, more preferably 2.5 to 8.6 μm, and even more preferably 2.5 to 8.3 μm. For example, it can be 2.5 to 7.7 μm, 2.5 to 7.3 μm, 2.5 Any one of ~6.9μm and 2.5~6.5μm.

The thickness (for example, T _a ) of the adhesive layer is not particularly limited as long as the conditions of the S value and the L value described above are satisfied. For example, the thickness of the adhesive layer may be 1.5-9 μm.

The "thickness of the adhesive layer" refers to the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive layer. From this point of view, the minimum and maximum thicknesses of the adhesive layer are determined.

The adhesive layer contains an adhesive. Examples of the adhesive include, for example, the adhesiveness of acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. The resin is preferably an acrylic resin.

In this specification, "adhesive resin" refers to the concept of including both adhesive resins and adhesive resins. For example, not only the resin itself has adhesive properties, but also includes the combination of additives and other components. On the other hand, resins showing adhesiveness, resins showing adhesion by the presence of a trigger 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 that the adhesive layer can be penetrated by the energy ray.

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

>>Adhesive composition>> The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition may be applied to the surface to be formed of the adhesive layer, dried if necessary, and an adhesive layer may be formed at the target site. The more specific method for forming the adhesive layer will be described in detail later together with the method for forming other layers. The ratio of the contents of the non-vaporized components at ordinary temperature in the adhesive composition is generally the same as the ratio of the contents of the above components of the adhesive layer.

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

The application of the adhesive composition can be performed by a conventional method, and examples include air knife coaters, blade coaters, rod coaters, gravure coaters, and roll coaters. Machine, roll coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, kiss coater Various coater methods such as kiss coater.

The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains the following solvent, it is preferably dried by heating. The adhesive composition containing a solvent is preferably dried at 70 to 130° C. for 10 seconds to 5 minutes, for example.

When the adhesive layer is energy ray-curable, the adhesive composition containing the energy ray-curable adhesive, that is, as the energy ray-curable adhesive composition, for example, those containing non-energy ray-curable Adhesive composition (I-1a) of adhesive resin (I-1a) (hereinafter sometimes simply referred to as "adhesive resin (I-1a)"), energy ray-curable compound; contained in non-energy ray-curable Adhesive resin (I-1a) has a side chain in which unsaturated groups are introduced into the energy ray-curable adhesive resin (I-2a) (hereinafter, sometimes simply referred to as "adhesive resin (I-2a)") Adhesive composition (I-2); Adhesive composition (I-3) containing the above-mentioned adhesive resin (I-2a), energy ray-curable compound, etc.

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

[Adhesive resin (I-1a)] The adhesive resin (I-1a) is preferably an acrylic resin. Examples of the acrylic resin include, for example, acrylic polymers having at least a structural unit derived from an alkyl (meth)acrylate. The structural units of the acrylic resin may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

Examples of the alkyl (meth)acrylate include, for example, those having an alkyl group having 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched. More specific examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (A Group) hexyl acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (methyl ) Tridecyl acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate) ), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), nineteen (meth)acrylate, arachidyl (meth)acrylate, etc.

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

The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate. Examples of the functional group-containing monomer include, for example, the functional group and the following cross-linking agent to become a starting point for cross-linking, the functional group and the unsaturated group in the unsaturated group-containing compound below It is possible to introduce unsaturated groups into the side chain of the acrylic polymer by reaction.

Examples of the functional group in the functional group-containing monomer include, for example, a hydroxyl group, a carboxyl group, an amine group, and an epoxy group. That is, examples of the functional group-containing monomer include, for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomers include, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3. -Hydroxyalkyl (meth)acrylates such as hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; ethylene Non-(meth)acrylic unsaturated alcohols such as alcohols and allyl alcohols (unsaturated alcohols that do not have a (meth)acryloyl skeleton) and the like.

Examples of the carboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, and Ethylene unsaturated dicarboxylic acids (condensation of dicarboxylic acids with ethylenically unsaturated bonds) such as carboxylic acid, maleic acid, citraconic acid, etc.; anhydrides of the above ethylenically unsaturated dicarboxylic acids; 2-carboxyl methacrylic acid Carboxyalkyl (meth)acrylates such as ethyl esters.

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

The functional group-containing monomer constituting the acrylic polymer may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

The above-mentioned acrylic polymer may have structural units derived from other monomers in addition to the structural units derived from the alkyl (meth)acrylate and the structural units derived from the functional group-containing monomer. The other monomers described above are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylate or the like. Examples of the other monomers mentioned above include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylic amide.

The other monomers constituting the acrylic polymer may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type, or two or more types, and if there are two or more types, these combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass relative to the total mass of the adhesive composition (I-1), and 10 to 10 95% by mass is better, and 15 to 90% by mass is particularly good.

[Energy Ray Hardening Compound] Examples of the energy ray-curable compound contained in the adhesive composition (I-1) include monomers or oligomers that have an energy ray polymerizable unsaturated group and can be cured by irradiation with energy ray. Among the energy ray-curable compounds, examples of the monomer include trimethylolpropane tri(meth)acrylate, neopentyl alcohol (meth)acrylate, neopentyl alcohol (meth)acrylic acid. Esters, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc. ) Acrylate; urethane (meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. Among the energy ray-curable compounds, examples of oligomers include, for example, oligomers obtained by polymerizing the monomers exemplified above. The energy ray-curable compound has urethane (meth)acrylate and urethane (methyl) from the viewpoint that the molecular weight is large and the storage modulus of the adhesive layer is difficult to decrease. Acrylic oligomers are preferred.

The above energy ray-curable compound contained in the adhesive composition (I-1) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

In the above adhesive composition (I-1), the content of the energy ray hardening compound is preferably 1 to 95% by mass relative to the total mass of the adhesive composition (I-1), and 5 to 90 The mass% is better, with 10~85 mass% being particularly good.

[Crosslinking agent] As the adhesive resin (I-1a), in addition to the structural unit derived from the alkyl (meth)acrylate, when the above acrylic polymer having the structural unit derived from the functional group-containing monomer is used, the adhesive is combined It is preferred that the substance (I-1) further contains a crosslinking agent.

The above-mentioned cross-linking agent is, for example, one that reacts with the above-mentioned functional group and cross-links the adhesive resins (I-1a). Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, stubble diisocyanate, and adducts of these diisocyanates. ); epoxy-based cross-linking agent such as ethylene glycol glycidyl ether (cross-linking agent with glycidyl group); hexa[1-(2-methyl)-aziridinyl]triphosphate trinitrogen Aziridine-based crosslinking agents such as heterobenzenes (crosslinking agents with aziridinyl groups); metal chelate-based crosslinking agents such as aluminum chelates (crosslinking agents with metal chelation structures); Isocyanurate-based crosslinking agent (crosslinking agent having isocyanurate skeleton) and the like. The isocyanate-based crosslinking agent is preferred from the viewpoint of improving the cohesive force of the adhesive agent and enhancing the adhesive force of the adhesive layer and being easily available.

The crosslinking agent contained in the adhesive composition (I-1) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

[Photopolymerization initiator] The adhesive composition (I-1) preferably contains a photopolymerization initiator. The adhesive composition (I-1) containing the photopolymerization initiator can perform sufficient hardening reaction even when irradiated with relatively low energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, and benzoin Benzoin compounds such as methyl benzoate and benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-di Acetophenone compounds such as methoxy-1,2-diphenylethane-1-one; bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2,4,6- Acetylphosphine oxide compounds such as trimethylbenzyldiphenylphosphine oxide; sulfide compounds such as benzyl phenyl sulfide, tetramethylthiuram monosulfide ; Α-keto alcohol compounds such as 1-hydroxycyclohexyl benzophenone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone (thioxanthone) etc. Thioxanthone compounds; peroxide compounds; diketone compounds such as diacetyl; benzyl; bibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane ; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl) phenyl] acetone; 2-chloroanthraquinone and so on.

The photopolymerization initiator contained in the adhesive composition (I-1) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and 0.03 to 10 parts by mass relative to 100 parts by mass of the above energy ray-curable compound. More preferably, 0.05 to 5 parts by mass is particularly preferred.

[Other additives] The adhesive composition (I-1) may contain other additives other than any of the components as long as the effect of the present invention is not impaired. Examples of the other additives mentioned above include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. Agents, reaction delay agents, crosslinking accelerators (catalysts) and other conventional additives. And, as a reaction delay agent, for example, the adhesive composition (I-1) in storage, the non-target crosslinking reaction due to the action of the catalyst mixed in the adhesive composition (I-1) is performed inhibition. As the reaction retarder, for example, a chelate complex is formed by chelating a catalyst, and more specifically, it has two or more carbonyl groups (-C(=O)- in one molecule). )By.

The other additives contained in the adhesive composition (I-1) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

[Solvent] The adhesive composition (I-1) may contain a solvent. Since the adhesive composition (I-1) contains a solvent, the coating suitability for the surface to be coated can be improved.

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

As the above-mentioned solvent, for example, it is possible to directly use the adhesive composition (I-1) without removing the user from the adhesive resin (I-1a) during the production of the adhesive resin (I-1a), The same or different type of solvent as the user used in the production of the adhesive resin (I-1a) may be additionally added during the production of the adhesive composition (I-1).

The solvent contained in the adhesive composition (I-1) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

>Adhesive composition (I-2)> As described above, the adhesive composition (I-2) contains an energy ray-curable adhesive resin (I-2a) having an unsaturated group introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a). ).

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

The above-mentioned unsaturated group-containing compound, in addition to the above energy ray polymerizable unsaturated group, further has a bond with the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a) Knot-based compounds. Examples of the energy ray polymerizable unsaturated group include, for example, (meth)acryloyl, vinyl (ethylene), propenyl (2-propenyl), etc., with (meth)acryloyl as the good. Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include, for example, isocyanate groups and epoxy groups that can be bonded to hydroxyl groups or amine groups, and groups that can be bonded to carboxyl groups or epoxy groups Bonded hydroxyl and amine groups.

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one kind, or two or more kinds, and if there are two or more kinds, the combination and ratio may be arbitrarily selected .

In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass relative to the total mass of the adhesive composition (I-2), and 10 to 10 95% by mass is better, and 10 to 90% by mass is particularly good.

[Crosslinking agent] As the adhesive resin (I-2a), for example, when using the same acrylic polymer having the structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1a), the adhesive composition (I -2) A crosslinking agent may be further contained.

Examples of the cross-linking agent in the adhesive composition (I-2) include the same as the cross-linking agent in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-2) may be only one kind, or two or more kinds, and if there are two or more kinds, the combination and ratio may be arbitrarily selected.

In the above-mentioned adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, and 0.1 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). For better, 0.3 to 15 parts by mass is particularly preferred.

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

Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-2) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-2), the content of the photopolymerization initiator relative to the content of the adhesive resin (I-2a) is 100 parts by mass, preferably 0.01 to 20 parts by mass, and 0.03 to 10 parts by mass Servings are more preferred, with 0.05 to 5 parts by mass being particularly preferred.

[Other additives] The adhesive composition (I-2) may contain other additives other than any of the above components as long as the effect of the present invention is not impaired. Examples of the other additives in the adhesive composition (I-2) include the same as the other additives in the adhesive composition (I-1). The other additives contained in the adhesive composition (I-2) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

[Solvent] The adhesive composition (I-2) may also contain a solvent for the same purpose as the adhesive composition (I-1). Examples of the solvent in the adhesive composition (I-2) include the same as the solvent in the adhesive composition (I-1). The solvent contained in the adhesive composition (I-2) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected. In the adhesive composition (I-2), the content of the solvent is not particularly limited, and may be appropriately adjusted.

>Adhesive composition (I-3)> As mentioned above, the said adhesive composition (I-3) contains the said adhesive resin (I-2a) and an energy ray hardening compound.

In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass relative to the total mass of the adhesive composition (I-3), and 10 to 10 95% by mass is better, and 15 to 90% by mass is particularly good.

[Energy Ray Hardening Compound] Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and can be hardened by irradiation with energy ray, and examples include , The same as the energy ray-curable compound contained in the adhesive composition (I-1). The energy ray-curable compound contained in the adhesive composition (I-3) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass, and preferably 0.03 to 100 parts by mass of the content of the adhesive resin (I-2a). 200 parts by mass is better, and 0.05 to 100 parts by mass is particularly good.

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

The photopolymerization initiator in the adhesive composition (I-3) may be the same as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-3), the content of the photopolymerization initiator is 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the above energy ray-curable compound. Preferably, 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.

[Other additives] The adhesive composition (I-3) may contain other additives other than any of the above-mentioned components within the range that does not impair the effects of the present invention. Examples of the other additives mentioned above include the same as the other additives in the adhesive composition (I-1). The other additives contained in the adhesive composition (I-3) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

[Solvent] The adhesive composition (I-3) may contain a solvent for the same purpose as the adhesive composition (I-1). Examples of the above-mentioned solvent in the adhesive composition (I-3) include the same as those in the adhesive composition (I-1). The solvent contained in the adhesive composition (I-3) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected. In the adhesive composition (I-3), the content of the solvent is not particularly limited, and may be appropriately adjusted.

>Adhesive composition other than adhesive composition (I-1) to (I-3)> So far, although the description is mainly on the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3), the content of the components described above, even if it is All adhesive compositions other than the three types of adhesive compositions (referred to as "adhesive compositions other than adhesive compositions (I-1) to (I-3)" in this specification) can also be the same To use.

Examples of the adhesive composition other than the adhesive compositions (I-1) to (I-3) include non-energy ray-curable adhesive compositions other than the energy-ray-curable adhesive composition. Examples of the non-energy ray-curable adhesive composition include, for example, acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, and polycarbonates. The adhesive composition (I-4) of a non-energy ray-curable adhesive resin (I-1a), such as an acrylic resin, is preferably an acrylic resin.

The adhesive composition other than the adhesive composition (I-1) to (I-3) preferably contains one or more crosslinking agents, and its content can be the same as that of the adhesive composition (I-1) ) The same at the same time.

>Adhesive composition (I-4)> Examples of the preferable adhesive composition (I-4) include those containing the above-mentioned adhesive resin (I-1a) and crosslinking agent.

[Adhesive resin (I-1a)] Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include 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 two or more types, and if there are two or more types, these combinations and ratios may be arbitrarily selected.

In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass relative to the total mass of the adhesive composition (I-4), and 10 to 10 95% by mass is better, and 15 to 90% by mass is particularly good.

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

[Crosslinking agent] As the adhesive resin (I-1a), in addition to the structural unit derived from the alkyl (meth)acrylate, the above-mentioned acrylic polymer having the structural unit derived from the functional group-containing monomer is further used, and the adhesive composition (I-4) It is preferable to further contain a crosslinking agent.

Examples of the crosslinking agent in the adhesive composition (I-4) include the same as the crosslinking agent in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-4) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

[Other additives] The adhesive composition (I-4) may contain other additives other than any of the above-mentioned components within the range that does not impair the effects of the present invention. Examples of the other additives mentioned above include the same as the other additives in the adhesive composition (I-1). The other additives contained in the adhesive composition (I-4) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

[Solvent] The adhesive composition (I-4) may contain a solvent for the same purpose as the adhesive composition (I-1). Examples of the above-mentioned solvent in the adhesive composition (I-4) include the same as those in the adhesive composition (I-1). The solvent contained in the adhesive composition (I-4) may be only one type, or two or more types, and if there are two or more types, these combinations and ratios may be arbitrarily selected. In the adhesive composition (I-4), the content of the solvent is not particularly limited, and may be appropriately selected.

In the above composite sheet for forming a protective film, the adhesive layer is preferably non-energy ray hardenable. This is because when the adhesive layer is energy ray curable, when the film for protective film formation is cured by irradiation of the energy ray, the adhesive layer cannot be simultaneously cured. If the adhesive layer and the protective film forming film are cured at the same time, the cured protective film forming film (ie, protective film) and the adhesive layer may be attached to the interface of the two to such an extent that they cannot be peeled off. At this time, it becomes difficult to peel off the semiconductor wafer including the protective film forming film after hardening, that is, the protective film (semiconductor wafer with protective film) from the support sheet including the adhesive layer after hardening, resulting in failure Pick up the semiconductor wafer with the protective film normally. In the above-mentioned support sheet, by making the adhesive layer non-energy ray hardenable, such improperness can be surely avoided, and the semiconductor wafer with a protective film can be picked up more easily.

Here, although the effect when the adhesive layer is non-energy ray hardening has been described, even if the layer directly in contact with the protective film forming film of the support sheet is a layer other than the adhesive layer, if this layer is non-energy ray hardening Sex, the same effect is achieved.

>>Manufacturing method of adhesive composition>> Adhesive compositions other than adhesive compositions (I-1) to (I-3), adhesive compositions (I-4) and other adhesive compositions (I-1) to (I-3) can be borrowed It is obtained by mixing the components other than the above-mentioned adhesive and components other than the above-mentioned adhesive as needed to constitute the adhesive composition. The order of addition during the preparation of each component is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent may be mixed with any formulation component other than the solvent to dilute the formulation component in advance, or may be used by mixing the solvent with these formulation components without diluting any formulation component other than the solvent in advance. The method of mixing the components at the time of preparation is not particularly limited, and the method of rotating and mixing the stirrer, the stirring blade, etc.; the mixing method using a mixer; the mixing method using ultrasonic waves, etc., may be appropriately selected from known methods. The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each formulated component does not deteriorate, and may be adjusted appropriately, but the temperature is preferably 15 to 30°C.

◎Protective film forming film The above-mentioned film for forming a protective film becomes a protective film in a state where it is cured or not cured. This protective film is for protecting the semiconductor wafer or the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer. The film for forming a protective film is soft and can be easily attached to the object to be attached.

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

In this specification, "non-hardening" refers to the property that it does not harden even by any means such as heating or irradiation of energy rays. In the present invention, even after the film for protective film formation is cured, as long as the laminated structure of the cured product of the support sheet and the film for protective film formation (in other words, the support sheet and protective film) is maintained, this laminate is called "protection" Composite sheet for film formation."

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

Here, referring to FIG. 4 again, the adhesive layer and the film for forming a protective film will be described in further detail. As previously explained, the first surface 11a of the base material 11 is a concave-convex surface. However, in the adhesive layer 12, the S value of 1.5 μm or more suppresses the influence of the uneven surface, and the unevenness on the first surface 12 a of the adhesive layer 12 decreases. Therefore, the lamination property between the adhesive layer 12 and the protective film forming film 13 becomes good. For example, between the adhesive layer 12 and the film 13 for forming a protective film, even if there are areas (non-bonding areas) 92 where the adhesive layer 12 and the film 13 for forming a protective film are not bonded, the number is formed in the entire protective film In the composite sheet 1A, the entire formation area of the protective film forming film 13 is less than 3 places. The non-lamination region 92 can be easily confirmed by viewing the composite sheet 1A for forming a protective film from the base 11 side, for example.

Furthermore, even if the composite sheet 1A for protective film formation has such a non-laminated region 92, the size (interlayer distance) of the non-laminated region 92 in the thickness direction of the composite sheet 1A for protective film formation is, for example, 0.5 μm or less In the composite sheet 1A for forming a protective film, the lamination property between the adhesive layer 12 and the film 13 for forming a protective film becomes better. Here, "the size of the non-lamination 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 interlayer distance) of the non-laminated area 92 is the same as the interlayer distance (size) of the non-laminated area 91, and is preferably 0.5 μm or less, for example, 0.4 μm or less, 0.3 μm or less, 0.2 μm Any of the following and 0.1 μm or less.

The size (interlayer distance) of the non-adhering region 92 can be obtained by the same method as the case of the size (interlayer distance) of the non-adhering region 91, except for the difference between the combinations of the two layers to be targeted, for example. .

In the composite sheet 1A for forming a protective film, the non-lamination area 92 may not exist at all.

On the other hand, as described above, the unevenness on the first surface 12a of the adhesive layer 12 becomes small. Therefore, although the thickness T _{p of the} protective film forming film 13 is not constant and varies depending on the location of the protective film forming film 13 (adhesive layer 12 ), the variation range is extremely small.

Furthermore, as described above, since the unevenness on the first surface 12a of the adhesive layer 12 becomes small, the surface (second surface) 13b of the protective film forming film 13 on the adhesive layer 12 side becomes smooth or the unevenness becomes small. Therefore, the appearance of the protective film forming film 13 is not damaged. Then, even in the protective film formed by the protective film forming film 13, the surface (second surface) on the side of the adhesive layer 12 becomes smooth or the unevenness becomes small, and the appearance of the protective film is not damaged. In this way, in the composite sheet 1A for forming a protective film, both the film 13 for forming a protective film and the protective film can become those with good design.

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

The above-mentioned maximum height difference on the second surface 13b of the protective film forming film 13 is formed, for example, by forming a cross section on the test piece of the protective film forming composite sheet or the protective film forming composite sheet itself by the method described previously. Scanning electron microscope (SEM) was observed by observing this section.

Here, although the composite sheet for forming a protective film 1A is taken as an example to describe the adhesive layer and the film for forming a protective film, the composite sheet for forming a protective film 1B, the composite sheet for forming a protective film 1C and other embodiments In the case of a composite sheet for forming a protective film, the film for forming an adhesive protective film is also the same.

In the composite sheet for forming a protective film of the present invention, the thickness (for example, T _p ) of the film for forming a protective film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the film for forming a protective film is equal to or greater than the above lower limit value, a protective film with higher protective ability can be formed. When the thickness of the protective film forming film is equal to or less than the above upper limit value, it can be suppressed from becoming excessively thick.

When the thickness of the protective film forming film varies depending on the position of the protective film forming film, the minimum value of the thickness of the protective film forming film may be equal to or greater than the above lower limit, and the maximum value of the thickness of the protective film forming film may also be Is below the upper limit.

In addition, the "thickness of the protective film forming film" refers to the thickness of the entire protective film forming film, for example, the thickness of the protective film forming film composed of a plurality of layers refers to all layers constituting the protective film forming film The total thickness of.

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

For example, by the method described previously, a test piece is cut out from a plurality of places (for example, 5 places) of the composite film for forming a protective film, and in this test piece, the minimum and maximum thickness of the film for forming the protective film is obtained , From these equivalent values, when the average value of the minimum value and the average value of the maximum value are obtained, the average value of the minimum value may be equal to or greater than the lower limit value of the thickness of the protective film forming film, The average value of may be equal to or less than the upper limit of the thickness of the protective film forming film.

The film for forming a protective film can be formed using a composition for forming a protective film containing its constituent material. For example, the protective film formation composition may be formed on a target portion by applying a protective film formation composition on the surface to be formed of the protective film formation film and drying it if necessary. The ratio of the contents of the non-vaporized components at normal temperature in the composition for forming a protective film is generally the same as the ratio of the contents of the aforementioned components in the film for forming a protective film.

The application of the protective forming composition can be performed by a conventional method, and examples include air knife coaters, blade coaters, rod coaters, gravure coaters, roll coaters, and rolls. Methods of various coaters such as knife coaters, curtain coaters, die coaters, knife coaters, screen coaters, Mailer bar coaters, and kiss coaters.

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 the following solvent, it is preferably dried by heating. Then, the composition for forming a protective film containing a solvent is preferably dried at 70 to 130° C. for 10 seconds to 5 minutes, for example. 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 film for forming a protective film will not be thermally cured.

Hereinafter, the film for protective film formation and the composition for protective film formation are explained in detail one by one.

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

After the film for forming a thermosetting protective film is attached to the back surface of the semiconductor wafer, the curing conditions at the time of thermal curing are not particularly limited as long as the cured product has a degree of curing that fully exerts its function, and corresponds to thermal curing The type of film for forming a protective film may be appropriately selected. For example, the heating temperature during thermosetting of the thermosetting protective film forming film is preferably 100 to 200°C, more preferably 110 to 180°C, and particularly preferably 120 to 170°C. Then, the heating time during the hardening is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.

>Composition for forming thermosetting protective film (III-1)> Examples of a preferred composition for forming a thermosetting protective film include, for example, a composition for forming a thermosetting protective film (III-1) containing a polymer component (A) and a thermosetting component (B) ( In this specification, it is abbreviated as "composition (III-1)") and the like.

[Polymer component (A)] The polymer component (A) is a component for imparting film-forming properties, flexibility, etc. in 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 kind, or two or more kinds, and if there are two or more kinds, you can choose this arbitrarily And other combinations and ratios.

Examples of the polymer component (A) include acrylic resins, polyesters, urethane resins, urethane acrylate resins, silicone resins, rubber resins, phenoxy resins, and thermosetting resins. Acrylic resins are preferred, such as polyimide.

Examples of the acrylic resin in the polymer component (A) include conventional acrylic polymers. The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is at least the above lower limit value, the shape stability of the film for forming a thermosetting protective film (time stability during storage) is improved. In addition, when the weight average molecular weight of the acrylic resin is equal to or less than the above upper limit, the film for forming a thermosetting protective film becomes easy to adhere to the uneven surface of the adherend, and the film for forming the adherend and the thermosetting protective film The occurrence of holes and the like is more suppressed.

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

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

Examples of the acrylic resin include, for example, one or more types of (meth)acrylate polymers; two or more types selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, Copolymers of monomers such as styrene and N-methylolacrylamide, etc.

Examples of the (meth)acrylate constituting the acrylic resin include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, ( Hexyl meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid N-nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (A Base) Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate ((meth) acrylate palm Ester), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is a chain having a carbon number of 1 to 18 Structured alkyl (meth)acrylate; (Meth)acrylic acid cyclopentyl (meth)acrylate, isocamphenyl (meth)acrylate, dicyclopentyl (meth)acrylate; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; Cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; (Meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicycloalkenyloxyethyl esters; (Meth)acrylic acid imide; (Meth)acrylates containing glycidyl groups such as glycidyl (meth)acrylate; Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy (meth)acrylate Hydroxyl-containing (meth)acrylates such as butyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; Substituted amine group-containing (meth)acrylates such as N-methylaminoethyl (meth)acrylate. Here, the "substituted amine group" refers to a group in which one or two hydrogen atoms of the amine group are substituted with groups other than hydrogen atoms.

The acrylic resin may, for example, be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc. other than the (meth)acrylate One or two or more monomers are copolymerized.

The monomer constituting the acrylic resin may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

The acrylic resin may also have functional groups that can bond with other compounds such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups. The above-mentioned functional group of the acrylic resin may be bonded to other compounds through the following crosslinking agent (F), or may be directly bonded to other compounds without the crosslinking agent (F). Since the acrylic resin is bonded to other compounds through the above functional groups, the reliability of the package obtained by using the composite film for forming a protective film tends to be improved.

In the present invention, as the polymer component (A), instead of using an acrylic resin, a thermoplastic resin other than the acrylic resin (hereinafter, simply referred to as "thermoplastic resin") may be used alone, or may be used together with the acrylic resin. By using the above-mentioned thermoplastic resin, the peelability of the protective film from the support sheet is improved, the film for forming a thermosetting protective film becomes easy to adhere to the uneven surface of the adherend, and the adherend is formed with the thermosetting protective film The occurrence of holes and the like between the membranes is more suppressed.

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

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

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

The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations may be arbitrarily selected And ratio.

In the composition (III-1), the content ratio of the polymer component (A) to the total content of all components except the solvent (that is, the polymer component (A) of the film for thermosetting protective film formation) Content), regardless of the type of polymer component (A), preferably 5 to 85% by mass, more preferably 5 to 75% by mass, for example, 5 to 65% by mass, 5 to 50% by mass and Any of 10 to 35% by mass.

The polymer component (A) may be compatible with the thermosetting component (B). In the present invention, when the composition (III-1) contains components corresponding to both the polymer component (A) and the thermosetting component (B), it is considered that the composition (III-1) contains the polymer component ( A) and thermosetting component (B).

[Thermosetting component (B)] The thermosetting component (B) is a component for curing the film for forming a thermosetting protective film. The composition (III-1) and the thermosetting component (B) contained in the film for forming a thermosetting protective film may be only one kind, or two or more kinds, and if two or more kinds, they may be arbitrarily selected These combinations and ratios.

Examples of the thermosetting component (B) include, for example, epoxy-based thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, silicone resin, etc., epoxy-based thermosetting resin Better.

(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 kind, or may be two or more kinds, and if two or more kinds, it may be arbitrarily selected These combinations and ratios.

Epoxy resin (B1) Examples of the epoxy resin (B1) include conventional ones, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-cresol novolac epoxy resins, Cyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type resin, etc., more than two functional epoxy compounds.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins having unsaturated hydrocarbon groups have higher compatibility with acrylic resins than resins having no unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the semiconductor wafer with a protective film obtained by using the composite film for forming a protective film is improved.

As the epoxy resin having an unsaturated hydrocarbon group, for example, a compound in which a part of the epoxy group of the multifunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such compounds can be obtained, for example, by addition reaction of (meth)acrylic acid or its derivatives to epoxy groups. In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include, for example, compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include methine (vinyl), 2-propenyl (propenyl), (meth)acryloyl, and (meth)acryloyl. Amino groups, etc. are preferably acryl.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but 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, it is 300 to 30,000 Good, 300~10000 is better, 300~3000 is especially good.

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

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

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

• Heat hardener (B2) The thermal hardener (B2) has a function as a hardener for the epoxy resin (B1). Examples of the thermosetting agent (B2) include compounds having two or more functional groups that can react with epoxy groups in one molecule. Examples of the above-mentioned functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amine groups, carboxyl groups, and acidified groups such as acid groups, and phenolic hydroxyl groups, amine groups or acid groups are preferably acidified groups. Phenolic hydroxyl or amine groups are more preferred.

Among the thermosetting agents (B2), examples of the phenolic curing agent having a phenolic hydroxyl group include, for example, polyfunctional phenol resin, biphenol, novolac type phenol resin, dicyclopentadiene type phenol resin, and aralkyl group. Type phenol resin, etc. Among the thermal hardeners (B2), examples of the amine-based hardener having an amine group include dicyandiamine and the like.

The thermal hardener (B2) may have an unsaturated hydrocarbon group. Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include, for example, a compound in which a part of the hydroxyl group of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin Based on the compound. The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.

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

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

One type of thermosetting agent (B2) may be used alone, or two or more types may be used in combination. If two or more types are used in combination, these combinations and ratios may be arbitrarily selected.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass relative to 100 parts by mass of the epoxy resin (B1). It is more preferably 1 to 200 parts by mass, for example, any one of 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 25 parts by mass, and 1 to 10 parts by mass. When the content of the thermosetting agent (B2) is equal to or greater than the above lower limit, curing of the film for forming a thermosetting protective film becomes easier. In addition, when the content of the thermosetting agent (B2) is equal to or lower than the upper limit, the moisture absorption rate of the film for forming a thermosetting protective film is reduced, and the reliability of the package obtained by using the composite sheet for forming a protective film is more reliable Promote.

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 The content of the polymer component (A) is 100 parts by mass, preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, further preferably 40 to 150 parts by mass, for example, 45 to 100 parts Any one of mass parts and 50 to 80 mass parts. When the content of the thermosetting component (B) is in this range, for example, the adhesive force between the cured product of the protective film forming film and the support sheet is suppressed, and the peelability of the support sheet is improved.

[Hardening accelerator (C)] The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening rate of the composition (III-1). Examples of preferred hardening accelerators (C) include, for example, tertiary amines such as triethylenediamine, dimethylbenzylamine, triethanolamine, dimethylamineethanol, and ginseng (dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (one or more) (Phosphines in which hydrogen atoms are replaced with organic groups); tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc.

The curing accelerator (C) 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, these may be arbitrarily selected The combination and ratio.

When the hardening accelerator (C) is used, the content of the hardening accelerator (C) in the composition (III-1) and the film for forming a thermosetting protective film is 100% by mass relative to the content of the thermosetting component (B) Parts, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass. When the above content of the hardening accelerator (C) is at least the above lower limit, the effect achieved by using the hardening accelerator (C) can be more remarkable. In addition, when the content of the hardening accelerator (C) is equal to or lower than the above upper limit, for example, the high-polarity hardening accelerator (C) is suppressed under high temperature and high humidity conditions in the film for forming a thermosetting protective film and The effect of the adhered body moving and segregating next to the interface side becomes higher, and the reliability of the semiconductor wafer with a protective film obtained by using the composite film for forming a protective film is further improved.

[Filling material (D)] The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). By containing the filler (D) in the film for forming a thermosetting protective film, it becomes easier to adjust the water absorption rate and the rate of change in adhesive force within the target range. In addition, since the film for forming a thermosetting protective film and the protective film contain a filler (D), the adjustment of the coefficient of thermal expansion becomes easier. For the film for forming a thermosetting protective film or the object to be formed of the protective film, This thermal expansion coefficient is optimized, and the reliability of the semiconductor wafer with a protective film obtained by using the composite film for forming a protective film is further improved. In addition, since the film for forming a thermosetting protective film contains a filler (D), the moisture absorption rate of the protective film can be reduced, and the heat dissipation can be improved.

The filler (D) may be either an organic filler or an inorganic filler, but it is preferably an inorganic filler. Examples of preferred inorganic fillers include powders of silicon oxide, alumina, talc, calcium carbonate, titanium white, Bengala, silicon carbide, and boron nitride. Sphericalized beads; surface modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silicon oxide or aluminum oxide, and more preferably silicon oxide.

The filler (D) 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, these may be arbitrarily selected The combination and ratio.

When the filler (D) is used, in the composition (III-1), the content ratio of the filler (D) to the total content of all components other than the solvent (that is, the film for thermosetting protective film formation) Content of the filler (D)), preferably 5 to 80% by mass, more preferably 10 to 70% by mass, for example, 20 to 65% by mass, 30 to 65% by mass and 40 to 65% by mass Either. With the content of the filler (D) in this range, the adjustment of the aforementioned thermal expansion coefficient becomes easier, and the strength of the protective film forming film and the protective film is further improved.

[Coupling agent (E)] The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). As the coupling agent (E), by using a functional group that can react with an inorganic compound or an organic compound, the adhesion and adhesion of the film for forming a thermosetting protective film to an adherend can be improved. In addition, by using the coupling agent (E), the cured product (protective film) of the thermosetting protective film forming film does not impair heat resistance and improves water resistance.

The coupling agent (E) is preferably a compound having a functional group that can react with the functional group possessed by the polymer component (A), thermosetting component (B), etc., and more preferably a silane coupling agent. Preferred examples of the above-mentioned silane coupling agent include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-cyclo Oxypropyloxypropyltriethoxysilane, 3-epoxypropyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3 -Methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2- (Aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltri Ethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxy Silane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, imidazolesilane, etc.

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

When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the film for forming a thermosetting protective film is relative to the polymer component (A) and the thermosetting component (B ) The total content is 100 parts by mass, preferably 0.03-20 parts by mass, more preferably 0.05-10 parts by mass, and particularly preferably 0.1-5 parts by mass. When the content of the coupling agent (E) is equal to or higher than the lower limit, the dispersibility of the filler (D) to the resin, the adhesion between the film for forming a thermosetting protective film and the adherend, etc. are improved by The effect achieved by using the coupling agent (E) becomes more significant. In addition, when the content of the coupling agent (E) is equal to or less than the above upper limit value, the occurrence of outgassing is further suppressed.

[Crosslinking agent (F)] As the polymer component (A), when the acrylic resin and the like having functional groups such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can be bonded to other compounds are used, The composition (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F). The crosslinking agent (F) is a component for bonding and crosslinking the above functional groups in the polymer component (A) with other compounds, and by such crosslinking, the film for forming a thermosetting protective film can be adjusted Initial adhesion and cohesion.

Examples of the crosslinking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate-based crosslinkers (crosslinkers with metal chelate structure), and aziridine-based crosslinkers. Linking agent (crosslinking agent with aziridine group), etc.

Examples of the organic polyvalent isocyanate compound 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.); terpolymers, isocyanurates and adducts of the above-mentioned aromatic polyvalent isocyanate compounds, etc.; and terminal isocyanate urethanes prepared by the reaction of the above-mentioned aromatic polyvalent isocyanate compounds and polyol compounds Polymer etc. The above-mentioned "adduct" means the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor Reaction products of low molecular weight active hydrogen-containing compounds such as sesame oil. Examples of the above-mentioned adducts include the following xylylene diisocyanate adducts of trimethylolpropane and the like. In addition, the "terminal isocyanate urethane prepolymer" is as previously explained.

As the organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4- Xylylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene di Isocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; all or part of polyols such as trimethylolpropane Hydroxyl, any one or more than two compounds of toluene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate; diamine isocyanate, etc.

Examples of the organic polyvalent imine compound include, for example, N,N′-diphenylmethane-4,4′-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β -Aziridinepropionate, tetramethylolmethane-tri-β-aziridinepropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) tri Ethyl melamine, etc.

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

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, and if there are two or more kinds, you may choose this And other combinations and ratios.

When the cross-linking agent (F) is used, the content of the cross-linking agent (F) of the composition (III-1) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the polymer component (A). It is more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. When the content of the cross-linking agent (F) is at least the above lower limit, the effect achieved by using the cross-linking agent (F) becomes more remarkable. In addition, when the content of the crosslinking agent (F) is equal to or less than the above upper limit, excessive use of the crosslinking agent (F) is suppressed.

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

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

Examples of the acrylate-based compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, neopentyltetraol tri(meth)acrylate, Neopentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth) (Meth) acrylate, 1,6-hexanediol di (meth) acrylate and other chain-containing aliphatic skeleton (meth) acrylate; dicyclopentyl di (meth) acrylate and other ring-containing Aliphatic (meth)acrylate; polyolefin glycol (meth)acrylate such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylate; urethane ( Meth)acrylate oligomer; epoxy modified (meth)acrylate; polyether (meth)acrylate other than the above polyolefin diol (meth)acrylate; itaconic acid oligomer, etc.

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

The above energy ray-curable compounds used in the polymerization may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

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

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

Examples of the photopolymerization initiator (H) in the composition (III-1) include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isopropyl Benzoin compounds such as butyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, benzoin dimethyl ketal, etc.; acetophenone, 2-hydroxy-2-methyl-1-phenyl- Acetophenone compounds such as propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis(2,4,6-trimethylbenzyl)benzene Phosphine oxide compounds such as benzyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide; sulfur such as benzyl sulfide benzene, tetramethyl methylsulfide carbamide sulfide Ether compounds; α-ketol compounds such as 1-hydroxycyclohexyl benzophenone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthones such as thioxanthone Compounds; peroxide compounds; diketones such as diacetyl; benzyl; bibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxyl -2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone, etc. In addition, examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone; and photosensitizers such as amines.

The photopolymerization initiator (H) contained in the composition (III-1) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

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

Examples of the organic pigments and organic dyes include, for example, ammonium pigments, cyanine pigments, merocyanin pigments, croconium pigments, squarylium pigments, and azulium pigments. Azulenium, polymethine, naphthoquinone, pyrylium, phthalocyanine, naphthalocyanine , Naphtholactam-based pigments (naphtholactam), azo-based pigments, condensed azo-based pigments, indigo-based pigments (indigo), cyperone-based pigments (perinone), perylene-based pigments (perylene), dioxazine Dioxazine, quinacridone, isoindolinone, quinophthalone, pyrrole, thioindigo , Metal complex dyes (metal salt dyes), dithiophenol metal complex dyes, indole phenol dyes, triarylmethane dyes, anthraquinone dyes (anthraquinone), di Oxazine pigments, naphthol pigments (naphthol), azomethine pigments (azomethine), benzimidazolone pigments (benzimidazolone), pyranthrone pigments (pyranthrone) and indanthrene pigments (indanthrene) Wait.

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

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

When the coloring agent (I) is used, the content of the coloring agent (I) of 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) of the film for forming a thermosetting protective film, by adjusting the light transmittance of the protective film, the legibility of the protective film during laser printing can be adjusted. In addition, by adjusting the content of the coloring agent (I) of the film for forming a thermosetting protective film and improving the designability of the protective film, it is also difficult to see the grinding marks on the back surface of the semiconductor wafer. In consideration of these, in the composition (III-1), the ratio of the content of the coloring agent (I) to the total content of all components other than the solvent (that is, the coloring agent (I ) Content), preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and particularly preferably 0.1 to 5% by mass. When the content of the colorant (I) is equal to or greater than the above lower limit, the effect achieved by using the colorant (I) becomes more remarkable. In addition, when the content of the colorant (I) is equal to or less than the upper limit value, the excessive decrease in light permeability of the film for forming a thermosetting protective film is suppressed.

[General Purpose Additive (J)] The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) within a range that does not impair the effect of the present invention. The general-purpose additive (J) may be a conventional one, and can be arbitrarily selected according to the purpose, and is not particularly limited, but preferred examples include plasticizers, antistatic agents, antioxidants, and adsorbents.

The general-purpose additive (J) 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, you can choose this arbitrarily And other combinations and ratios. The content of the general-purpose additive (J) of the composition (III-1) and the film for thermosetting protective film formation is not particularly limited, and may be appropriately selected according to the purpose.

[Solvent] It is preferable that the composition (III-1) further contains a solvent. The composition (III-1) containing the solvent has good handleability. The above solvent is not particularly limited, but preferred ones include, for example, hydrocarbons such as toluene and stubble; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1 -Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond )Wait. The solvent contained in the composition (III-1) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

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

>>Production method of thermosetting protective film forming composition>> The composition for forming a thermosetting protective film such as the composition (III-1) can be obtained by blending the components that constitute it. In the preparation of each component, the order of addition is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent may be mixed with any formulation component other than the solvent to dilute the formulation component in advance, or may be used by mixing the solvent with these formulation components without diluting any formulation component other than the solvent in advance. The method of mixing the components at the time of preparation is not particularly limited, and the method of rotating and mixing the stirrer, the stirring blade, etc.; the mixing method using a mixer; the mixing method using ultrasonic waves, etc., may be appropriately selected from known methods. The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each formulated component does not deteriorate, and may be adjusted appropriately, but the temperature is preferably 15 to 30°C.

○Energy ray-curable protective film forming film Examples of the film for forming an energy ray curable protective film include those containing an energy ray curable component (a), and those containing an energy ray curable component (a) and a filler are preferred. In the film for forming an energy ray-curable protective film, the energy ray-curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive. Here, "energy ray" and "energy ray hardenability" are as previously explained.

After the film for forming an energy ray-curable protective film is attached to the back surface of a semiconductor wafer, curing conditions for curing are not particularly limited as long as the cured product can achieve a degree of curing that fully exerts its function. The type of film for forming a protective film may be appropriately selected. For example, when curing the film for forming an energy ray-curable protective film, the illuminance of the energy ray is preferably 120 to 280 mW/cm ² . Then, in the above hardening, the amount of light of the energy ray is preferably 100 to 1000 mJ/cm ² .

>Energy ray-hardenable protective and non-forming composition (IV-1)> Examples of the preferred composition for forming an energy ray curable protective film include, for example, the composition for forming an energy ray curable protective film (IV-1) containing the aforementioned energy ray curable component (a) (in this specification In some cases, it is abbreviated as "composition (IV-1)").

[Energy ray hardening component (a)] The energy ray-curable component (a) is a component that is cured by irradiation of energy ray, and is used to impart film-forming properties, flexibility, etc. to the film for forming an energy ray-curable protective film, while forming hard protection after curing The composition of the membrane. Examples of the energy ray-curable component (a) include, 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 having an energy ray-curable group and a molecular weight of 100 to 80,000 (a2). The above-mentioned polymer (a1) may be cross-linked by a cross-linking agent in at least a part thereof, or may be one without cross-linking.

(Polymer (a1) with an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000) Examples of the polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000 include, for example, an acrylic polymer (a11) having a functional group that can react with groups that other compounds have, and An acrylic resin (a1-1) obtained by reacting an energy ray-curable compound (a12) having an energy ray-curable group such as a group reactive with the functional group and an energy ray-curable double bond.

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

•Acrylic polymer with functional groups (a11) Examples of the acrylic polymer (a11) having the above functional group include, for example, those obtained by copolymerizing an acrylic monomer having the above functional group with an acrylic monomer not having the above functional group, etc. In addition to monomers, monomers other than acrylic monomers (non-acrylic monomers) may be copolymerized. In addition, the acrylic polymer (a11) may be a random copolymer or a block copolymer, and a conventional method can be used for the polymerization method.

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

Examples of the hydroxyl group-containing monomers include, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3. -(Meth)acrylate hydroxyalkyl such as hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; ethylene Non-(meth)acrylic unsaturated alcohols such as alcohols and allyl alcohols (unsaturated alcohols that do not have a (meth)acryloyl skeleton) and the like.

Examples of the carboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond); fumaric acid, and Ethylene unsaturated dicarboxylic acids (condensation of dicarboxylic acids with ethylenically unsaturated bonds) such as carboxylic acid, maleic acid, citraconic acid, etc.; anhydrides of the above ethylenically unsaturated dicarboxylic acids; 2-carboxyl methacrylic acid Carboxyalkyl (meth)acrylates such as ethyl esters.

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

The acrylic monomer constituting the acrylic polymer (a11) and having the functional group may be only one type, or two or more types, and if there are two or more types, these combinations and ratios may be arbitrarily selected.

Examples of the acrylic monomer that does not have the above functional group include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate , N-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth) ) Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate Ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (meth) Tridecyl acrylate, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate) , The alkyl group constituting the alkyl ester, such as heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc., has a chain structure of 1 to 18 carbon atoms ( Alkyl methacrylate etc.

In addition, examples of the acrylic monomer that does not have the aforementioned functional group include, for example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxy (meth)acrylate. Alkoxyalkyl group-containing (meth)acrylates such as methyl ester, ethoxyethyl (meth)acrylate, etc.; aryl (meth)acrylates such as phenyl (meth)acrylate, etc., have aromatic Group-based (meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N , N-dimethylaminopropyl esters, etc. (meth)acrylates with non-crosslinkable tertiary amino groups.

The acrylic monomer that constitutes the acrylic polymer (a11) and does not have the functional group may be only one type, or two or more types, and if there are two or more types, these combinations and ratios may be arbitrarily selected .

Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; and styrene. The non-acrylic monomer constituting the acrylic polymer (a11) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected.

In the acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the functional group with respect to the total amount of the structural unit constituting it is 0.1 to 50% by mass as It is better, 1 to 40% by mass is better, and 3 to 30% by mass is particularly good. With these ratios in these ranges, in the acrylic resin (a1-1) obtained by copolymerizing the acrylic polymer (a11) and the energy ray-curable compound (a12), the energy ray-curable The content of the base becomes easy to adjust the degree of hardening of the protective film to a preferable range.

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type, or two or more types, and if there are two or more types, these combinations and ratios may be arbitrarily selected.

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

•Energy ray hardening compound (a12) The energy ray-curable compound (a12), as a group reactive with the functional group of the acrylic polymer (a11), has one or two selected from the group consisting of isocyanate groups, epoxy groups, and carboxyl groups More than one kind is preferable. As the above-mentioned group, those having an isocyanate group are more preferable. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

The energy ray curable compound (a12) is preferably one having 1 to 5 energy ray curable groups per molecule, and more preferably 1 to 3.

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

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one kind, or two or more kinds, and if there are two or more kinds, these combinations and ratios may be arbitrarily selected .

In the acrylic resin (a1-1), relative to the content of the functional group derived from the acrylic polymer (a11), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) , Preferably 20 to 120 mol%, 35 to 100 mol% is even better, and 50 to 100 mol% is especially good. When the ratio of the content is within these ranges, the adhesion of the protective film after hardening becomes greater. In addition, when the energy ray-curable compound (a12) is a monofunctional (having one of the above groups in one molecule) compound, although the upper limit of the content ratio is 100 mol%, when the energy ray is hardened When the sexual compound (a12) is a polyfunctional (having two or more of the above groups in one molecule) compound, the upper limit of the content ratio may exceed 100 mol%.

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

When the polymer (a1) is crosslinked with at least a part of it by a crosslinking agent, the polymer (a1) may not be described as equivalent to those constituting the acrylic polymer (a11) A monomer having any of the above monomers and having a group that reacts with a crosslinking agent is polymerized and crosslinked with the group that reacts with the crosslinking agent, or may be derived from the above energy ray-curable compound (a12) , It is formed by crosslinking the above groups that react with the functional groups.

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 kind, or two or more kinds, and if two or more kinds, they may be arbitrarily selected These combinations and ratios.

(Compound (a2) with an energy ray-curable group and a molecular weight of 100 to 80,000) Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred ones include (methyl) Acryloyl, vinyl, etc.

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

Among the above compounds (a2), examples of the low-molecular-weight compound having an energy ray-curable group include polyfunctional monomers and oligomers, and the acrylate-based compound having a (meth)acryloyl group is preferred. . Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylation. Ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A Di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(methyl ) Propylene acetyloxyethoxy) phenyl] stilbene, 2,2-bis[4-((meth)acryl oxypolypropyloxy) phenyl] propane, tricyclodecane dimethanol di( Meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (Meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxyethyl Oxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryl 2-functional (meth)acrylates such as oxypropane; Ginseng (2-(meth)acryloyloxyethyl) isocyanurate, ε-caprolactone modified Ginseng-(2-(meth)acryloyloxyethyl)isocyanuric acid Ester, ethoxylated glycerol tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate Methacrylates, ethoxylated neopentaerythritol tetra(meth)acrylates, neopentaerythritol tetra(meth)acrylates, dipentaerythritol poly(meth)acrylates, dineopentyl Multifunctional (meth)acrylates such as tetraol hexa(meth)acrylate; Multifunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers and the like.

Among the above compounds (a2), as the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group, for example, the description in Paragraph 0043 of "Japanese Patent Laid-Open No. 2013-194102" can be used. By. Although this type of resin conforms to the resin constituting the thermosetting component described below, it is adopted as the above-mentioned compound (a2) in the present invention.

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

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

[Polymer (b) without energy ray-curable group] The composition (IV-1) and the film for forming an energy ray-curable protective film, when containing the compound (a2) as the energy ray-curable component (a), further contain a polymer having no energy ray-curable group (b) is better. The above polymer (b) may be cross-linked by at least a part of it with a cross-linking agent, or it may be There is no cross-linker.

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

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

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include, for example, alkyl (meth)acrylate, (meth)acrylate having a cyclic skeleton, and epoxy-containing (Meth)acrylate, hydroxyl-containing (meth)acrylate, substituted amine group-containing (meth)acrylate, etc. Here, the "substituted amine" group is as previously described.

Examples of the above-mentioned alkyl (meth)acrylate include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, N-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate , Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (meth)acrylic acid Tridecyl ester, myristyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate), The alkyl group constituting the alkyl ester, such as heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc., has a chain structure of 1 to 18 carbon atoms (a Group) alkyl acrylate, etc.

Examples of the (meth)acrylate having a cyclic skeleton include, for example, cycloalkyl (meth)acrylate such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; (Meth)acrylate dicyclopentenyl and other (meth)acrylate cycloalkenyl esters; Cycloalkenyloxyalkyl (meth)acrylate and the like, such as dicycloalkenyloxyethyl (meth)acrylate.

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

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

Examples of the polymer (b) that is crosslinked with at least a part by a crosslinking agent and does not have the energy ray-curable group include, for example, a reactive functional group in the polymer (b) and a crosslinking agent react to Successful. The reactive functional group is not particularly limited as long as it is appropriately selected according to the type of crosslinking agent and the like. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional group may include a hydroxyl group, a carboxyl group, an amine group, and the like. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. In addition, when the crosslinking agent is an epoxy-based compound, examples of the reactive functional group include a carboxyl group, an amine group, and an amide group. Among these, a carboxyl group having high reactivity with an epoxy group is preferred. However, from the viewpoint of preventing corrosion of the semiconductor wafer and the circuit of the semiconductor wafer, the reactive functional group is preferably a group other than the carboxyl group.

Examples of the polymer (b) having the above-mentioned reactive functional group and not having an energy ray-curable group include, for example, those obtained by polymerizing monomers having at least the above-mentioned reactive functional group. In the case of the acrylic polymer (b-1), any or both of the above-mentioned acrylic monomers and non-acrylic monomers constituting these monomers have been cited as long as they have the above-mentioned reactive function The base can be. Examples of the above-mentioned polymer (b) having a hydroxyl group as a reactive functional group include, for example, those obtained by polymerizing hydroxyl-containing (meth)acrylates, and other than those listed above, Among the acrylic monomers or non-acrylic monomers, monomers in which one or more hydrogen atoms are substituted with the reactive functional groups are obtained by polymerization.

In the above-mentioned polymer (b) having a reactive functional group, the ratio (content) of the amount of structural units derived from the monomer having a reactive functional group relative to the total amount of the structural units constituting these is 1 ~20% by mass is better, and 2~10% by mass is even better. With the above ratio in such a range, the degree of crosslinking in the polymer (b) becomes a better range.

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

The polymer (b) contained in the composition (IV-1) and the film for forming an energy ray-curable protective film, which does not have an energy ray-curable group, may be only one kind, or may be two or more kinds, if it is two In the case of more than one species, these combinations and ratios can be arbitrarily selected.

Examples of the composition (IV-1) include either or both of the polymer (a1) and the compound (a2). Then, when the composition (IV-1) contains the above-mentioned compound (a2), it is preferable to further contain the polymer (b) having no energy ray-curable group, and in this case, it is more preferable to further contain the above-mentioned (a1). In addition, the composition (IV-1) may not contain the above-mentioned compound (a2), but also contain the above-mentioned polymer (a1) and the polymer (b) having no energy ray-curable group.

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

In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (also That is, the total content of the energy ray curable component (a) and the polymer (b) having no energy ray curable group in the film for forming an energy ray curable protective film) is preferably 5 to 90% by mass, and 10 to 80% by mass is better, and 20 to 70% by mass is particularly preferable. With the above ratio of the content of the energy ray-curable component being in these ranges, the energy ray-curability of the film for forming an energy ray-curable protective film becomes better.

In addition to the above energy ray-curable components, the composition (IV-1) may contain a heat-curable component, a filler, a coupling agent, a cross-linking agent, a photopolymerization initiator, a colorant, and a general-purpose additive for the purpose One or more than one of the group.

For example, by using the composition (IV-1) containing the above energy ray-curable component and thermosetting component, the formed energy ray-curable protective film forming film is heated to enhance the adhesion to the adherend As a result, the strength of the protective film formed by the film for forming an energy ray-curable protective film is also improved. In addition, by using the composition (IV-1) containing the above energy ray-curable component and the coloring agent, the formed energy ray-curable protective film-forming film is shown to be the same as the thermal-curable protective film-forming method described previously. When the film contains a coloring agent (I), it has the same effect.

Examples of the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, colorant, and general-purpose additive in the composition (IV-1) include the composition (III-1) ) In the thermosetting component (B), filler (D), coupling agent (E), crosslinking agent (F), photopolymerization initiator (H), colorant (I) and general additives (J ) The same.

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

The content of the above thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, coloring agent and general-purpose additive in the composition (IV-1) may be appropriately selected according to the purpose, and No particular limitation.

From the viewpoint of improving the operability by dilution, it is preferable that the composition (IV-1) further contains a solvent. The solvent contained in the composition (IV-1) may, for example, be the same as the solvent in the above-mentioned composition (III-1). The solvent contained in the composition (IV-1) may be only one kind or two or more kinds.

>>Method for manufacturing composition for forming energy ray curable protective film>> The composition for forming an energy ray-curable protective film such as the composition (IV-1) can be obtained by blending the components that constitute these. The order of addition during the preparation of each component is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent may be mixed with any formulation component other than the solvent to dilute the formulation component in advance, or may be used by mixing the solvent with these formulation components without diluting any formulation component other than the solvent in advance. The method of mixing the components at the time of preparation is not particularly limited, and the method of rotating and mixing the stirrer, the stirring blade, etc.; the mixing method using a mixer; the mixing method using ultrasonic waves, etc., may be appropriately selected from known methods. The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each formulated component does not deteriorate, and may be adjusted appropriately, but the temperature is preferably 15 to 30°C.

○Non-curable protective film forming film Although the film for forming a non-curable protective film does not show a change in characteristics due to curing, in the present invention, it is considered that a protective film has been formed at a stage where it has been attached to the back surface of the semiconductor wafer or the like as a target .

Examples of preferred films for forming a non-curable protective film include, for example, those containing thermoplastic resins.

>Composition for forming non-curing protective film (V-1)> Examples of the composition for forming a non-curable protective film include, for example, a composition (V-1) for forming a non-curable protective film containing the above-mentioned thermoplastic resin (in this specification, it is sometimes simply referred to as "composition ( V-1)") etc.

[Thermoplastic resin] The thermoplastic resin is not particularly limited. As the thermoplastic resin, more specifically, for example, acrylic resins, polyesters, polyurethanes, phenoxy resins, polybutene, and acrylic resins listed as the components of the composition (III-1), Non-curable resins such as polybutadiene and polystyrene are the same.

The above-mentioned thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be only one kind, or two or more kinds, and if there are two or more kinds, these may be arbitrarily selected Combination and ratio.

In the composition (V-1), the ratio of the content of the thermoplastic resin relative 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), It is preferably 5 to 90% by mass. For example, it may be any of 10 to 80% by mass and 20 to 70% by mass.

In addition to the above thermoplastic resins, the composition (V-1) may contain one or more types selected from the group consisting of fillers, coupling agents, crosslinking agents, colorants, and general-purpose additives, depending on the purpose.

For example, by using the composition (V-1) containing the above thermoplastic resin and coloring agent, the formed film for forming a non-curable protective film shows that the film for forming a thermosetting protective film described above contains coloring The same effect as the agent (I).

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

In the composition (V-1), the filler, coupling agent, crosslinking agent, colorant and general-purpose additive may be used alone or in combination of two or more. When two or more are used in combination, Arbitrarily choose these combinations and ratios.

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

From the viewpoint of improving the operability by dilution, it is preferable that the composition (V-1) further contains a solvent. Examples of the solvent contained in the composition (V-1) include the same as the solvent in the above-mentioned composition (III-1). The solvent contained in the composition (V-1) may be only one kind or two or more kinds.

>>Manufacturing method of non-curing protective film forming composition>> The composition for forming a non-curable protective film such as the composition (V-1) can be obtained by blending the components used to constitute these. The order of addition during the preparation of each component is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent may be mixed with any formulation component other than the solvent to dilute the formulation component in advance, or may be used by mixing the solvent with these formulation components without diluting any formulation component other than the solvent in advance. The method of mixing the components at the time of preparation is not particularly limited, and the method of rotating and mixing the stirrer, the stirring blade, etc.; the mixing method using a mixer; the mixing method using ultrasonic waves, etc., may be appropriately selected from known methods. The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each formulated component does not deteriorate, and may be adjusted appropriately, but the temperature is preferably 15 to 30°C.

◎Other layers The support sheet may include other layers such as the intermediate layer in addition to the base material and the adhesive layer as long as the effect of the present invention is not impaired. In addition, the 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 as long as the effects of the present invention are not impaired, and the other layers in this case may include a support The other layers of the sheet may be arranged without directly contacting the support sheet. The other layers mentioned above can be arbitrarily selected according to the purpose, and the types are not particularly limited.

As an embodiment of the composite sheet for forming the support sheet and the protective film, for example, the adhesive layer is non-energy ray-curable, and the adhesive layer contains at least a structural unit derived from an alkyl (meth)acrylate. In the adhesive layer, the acrylic polymer and the crosslinking agent have a crosslinking agent content of 0.3 to 50 parts by mass relative to 100 parts by mass of the acrylic polymer, and the first side of the substrate The maximum height roughness (Rz) is 0.01 to 8 μm.

As an embodiment of the composite sheet for forming the support sheet and the protective film, for example, the adhesive layer is non-energy ray-curable, and the adhesive layer contains at least a structural unit derived from an alkyl (meth)acrylate. In the adhesive layer, the acrylic polymer and the crosslinking agent have a crosslinking agent content of 0.3 to 50 parts by mass relative to 100 parts by mass of the acrylic polymer, and the acrylic polymer has an alkyl group A structural unit derived from an alkyl (meth)acrylate having a carbon number of 4 or more and a structural unit derived from a monomer containing a hydroxyl group, and the maximum height roughness (Rz) of the first surface of the base material is 0.01 to 8 μm .

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

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

◇Manufacturing method of composite sheet for forming protective film The above-mentioned composite film for forming a protective film may have, for example, a step of producing a laminated sheet formed by laminating a substrate, an adhesive layer and a film for forming a protective film in this order (in this specification) , Sometimes referred to as "lamination sheet manufacturing step (1)"), manufacturing the step of pressing and storing the above laminate sheet in its thickness direction (in this specification, it is sometimes referred to as "lamination sheet preservation step") Method (sometimes referred to as "manufacturing method (S1)" in this specification). The formation method of each layer (base material, adhesive layer, and protective film forming film) is as previously explained. Hereinafter, the above-described manufacturing method (S1) will be described in more detail for each step.

◎Manufacturing method (S1) >>Procedures for production of laminates (1)>> In the above-mentioned laminated sheet production step (1), a laminated sheet is produced in which the base material, the adhesive layer, and the film for forming a protective film are laminated in this order in the thickness direction. 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.), the same as the target composite film forming protective film Laminated slices of laminated structure. In addition, in this specification, the "lamination sheet", unless otherwise specified, means a person having the same lamination structure as the above-mentioned composite sheet for forming a protective film, and has not performed the lamination sheet preservation step.

For example, when manufacturing the support sheet, when the adhesive layer is laminated on the substrate, the adhesive composition may be coated on the substrate and dried as necessary.

On the other hand, for example, when a film for forming a protective film is further laminated on the adhesive layer that has been laminated on the base material, the composition for forming a protective film may be coated on the adhesive layer to directly form the film for forming a protective film . For a layer other than the film for forming a protective film, a composition for forming this layer can also be used, and this layer is laminated on the adhesive layer by the same method. In this way, when any one of the compositions is used to form a continuous two-layer build-up structure, a new layer can be formed by further applying the composition on the layer formed from the above composition. However, by forming the post-stacked layer of these two layers, the pre-formed composition is preliminarily formed on another release film, and the exposed surface of the layer formed thereon opposite to the side in contact with the release film, It is preferable to bond with the exposed surface of the remaining layer that has been formed, and to form a stacked structure of two consecutive layers. At this time, the above composition is preferably applied to the peeling treatment surface of the peeling film. After the release film is formed, it can be removed as needed.

For example, when manufacturing a composite film for forming a protective film formed by laminating an adhesive layer on a substrate and laminating a protective film forming film on the adhesive layer (the support sheet is a protective film of a laminate of a substrate and an adhesive layer) When forming a composite sheet), by applying the adhesive composition on the base material, drying it if necessary, and stacking the adhesive layer on the base material; in addition, by applying a protective film forming combination on the release film If necessary, it is dried, and a film for forming a protective film is formed on the release film. Then, by bonding the exposed surface of the protective film forming film to the exposed surface of the adhesive layer laminated on the substrate, 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 the release film and dried if necessary. An adhesive layer is formed on the release film, and the exposed surface of this layer is bonded to the surface on the side of the substrate, thereby laminating the adhesive on the substrate. In either method, the release film can be removed at any time after the formation of the target laminate structure.

In this way, any layer other than the base material constituting the composite sheet for forming a protective film can be laminated by a method previously formed on the release film and bonded to the surface of the target layer, so it can be appropriately selected and adopted as necessary Such steps are used to manufacture the above laminates.

For example, the composite sheet for forming a protective film is usually stored by bonding the release film to the surface of the outermost layer (for example, the film for forming a protective film) on the side opposite to the support sheet. Therefore, by applying a composition for forming the outermost layer, such as a composition for forming a protective film, on this release film (preferably its release-treated surface), it is dried as necessary, and the release film Form the topmost layer, and on the exposed surface of the layer opposite to the side in contact with the release film, the remaining layers are laminated by any of the above methods. The release film is maintained in a bonded state without removal to obtain the above Laminate.

When the composite sheet for forming a protective film includes the above-mentioned other layer, the step of providing the above-mentioned other layer may be appropriately performed at an appropriate point in time in the step (1) of producing the laminated sheet so as to be an appropriate arrangement position.

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

>>Steps to save the laminated film>> In the lamination sheet storage step, the lamination sheet is pressed while being stored in its thickness direction. In this step, as a method of pressing and storing the laminate sheet, for example, a long strip of the laminate sheet is wound into a roll shape, and the wound laminate sheet is rolled in this state by rolling Take the generated pressure, pressurize one side or both sides of the laminate and store it; the roll of the above laminate is not rolled into a roll, the laminate in the unfolded state, or, in the non-strip One or both sides of the above-mentioned laminated sheet, a method of applying pressure and storing, etc.

When the long laminated sheet is wound in a roll shape, the laminated sheet is preferably wound in the longitudinal direction. When winding the laminate, for example, a winding tension of 150 to 170 N/m is preferred, a winding speed of 45 to 55 m/min is preferred, and the pull-out ratio (attenuation rate) of the winding tension is preferably 85 to 95% By using these winding conditions, the laminated sheet can be stored under pressure at a more appropriate pressure. These winding conditions are particularly suitable for, for example, a laminate having a thickness of 100 to 300 μm, a width of 300 to 500 mm, and a length of 40 to 60 m, but the size of the laminate is not limited to this.

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

The laminated sheet wound into a roll shape can be stored at room temperature or room temperature, but it is preferably heated and stored. By heating and pressurizing storage, a laminate sheet for protective film formation with better legibility of a protective film or a protective film or a film for protective film formation via a support sheet can be obtained by laminating between the adhesive layer and the protective film forming film .

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

The storage time when the laminated sheet has been wound into a roll is not particularly limited, but it is preferably 24 to 720 hours (1 to 30 days), and more preferably 48 to 480 hours (2 to 20 days). 72~240 hours (3~10 days) is especially good.

The laminated sheet wound into a roll shape may, for example, process a film for forming a protective film and a support sheet into a specific shape, and a plurality of laminates of the film for forming the supporting sheet and the protective film thus processed may be On the film side for forming a protective film, a long release film is bonded, and the release film is arranged in the longitudinal direction of the release film. In this case, the film for forming a protective film is preferably one having the same or almost the same planar shape (usually circular) as the semiconductor wafer. In addition, it is preferable that the support piece at this time has the same or almost the same outer peripheral shape as the jig for fixing the support piece in the cutting device. In addition, in this case, it is preferable to provide a strip-shaped sheet so that the laminate surface of the release film does not overlap the laminate in the vicinity of the peripheral portion in the short-side direction. This sheet is used to suppress the occurrence of a level difference (sometimes referred to as a "lamination mark" in the present specification) on the surface of the laminate when the laminate sheet is wound into a roll shape. The above-mentioned lamination marks are due to the fact that in the roller of the lamination sheet, the lamination position of the lamination object (the lamination object of the processed support sheet and the film for forming a protective film) does not match in the radial direction of the roller and is applied on the surface of the lamination object Produced under high pressure. If the sheet is provided in the vicinity of the peripheral portion, such a high pressure is not applied to the surface of the laminate, and the occurrence of the laminate mark is suppressed.

When the long laminated sheet is not wound into a roll shape and is in an unfolded state, and when the laminated sheet is a non-long sheet, it is preferable to further store and store a plurality of these laminated sheets. Then, when laminating the lamination sheets in this way, it is preferable that the directions of the plurality of lamination sheets and the positions of the surrounding parts are aligned with each other.

The shape and size of the non-strip laminate (in other words, a single laminate) are not particularly limited. For example, in a manner suitable for processing one semiconductor wafer using a dicing device, adjust the shape of the lamination sheet according to the shape and size of the semiconductor wafer and the shape and size of the jig for fixing the support piece in the dicing device And the size is better.

The above-mentioned laminated sheet in a layered state can be stored at normal temperature or room temperature, preferably at the same time when heated. By such heat and pressure preservation, it is possible to obtain a laminate film between the adhesive layer and the film for forming a protective film, and a protective film for forming a protective film with better legibility of the protective film or the film for forming the protective film through the support sheet Composite sheet. In addition, when the laminated sheet in the laminated state is stored under pressure, any one of the heating temperature and the storage time may be the same as when the laminated sheet is wound in a roll shape.

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

In the manufacturing method (S1) of the laminated sheet manufacturing step (1), the order of lamination (lamination) of the substrate, the adhesive layer, and the protective film forming film is not particularly limited, but the support sheet (on the substrate) is prepared in advance Pre-laminate an adhesive layer), prepare a film for forming a protective film in advance, and deposit a film for forming a protective film on a supporting sheet, either or both of the supporting sheet and the film for forming a protective film may be used separately. Before stacking, it was stored under pressure by the same method as the above-mentioned stacking sheet. By separately storing the supporting sheet before lamination under pressure, the occurrence of the above-mentioned non-bonding area between the base material and the adhesive layer can be more effectively suppressed. In addition, by separately storing the protective film forming film before lamination under pressure, the unevenness of the surface (second surface) of the protective film forming film and the adhesive layer side of the protective film becomes smaller (the smoothness becomes larger) ) To improve the design of the protective film forming film and protective film.

That is, the above-mentioned composite film for forming a protective film can also be manufactured by, for example, a manufacturing method having the following steps (in this specification, it is sometimes referred to as "manufacturing method (S2)"): by having a substrate in the laminate And the above-mentioned adhesive layer of the supporting sheet of the adhesive layer, a film for forming a protective film is laminated, and a substrate, an adhesive layer and a film for forming a protective film are laminated in this order in the thickness direction to produce a laminated sheet Step (in this specification, it is sometimes referred to as "layered sheet manufacturing step (2)"); step of pressing and storing the above layered sheet in its thickness direction (storage step); further having the above layered sheet manufacturing step ( 2) Before, either or both of the above-mentioned support sheet and the film for forming a protective film are pressed while being stored in the thickness direction (in this specification, the step of storing the support sheet is called "support sheet storage" "Step", a step of storing the film for forming a protective film, is called "a film storing step for forming a protective film").

◎Manufacturing method (S2) In the above manufacturing method (S2), the lamination sheet production step (2) is performed as the lamination sheet production step (1), and besides, either one of the above support sheet storage step and the protective film formation film storage step or Except for the difference between the two, the rest is the same as the above-mentioned manufacturing method (S1).

>>Procedures for production of laminates (2)>> The above-mentioned lamination sheet manufacturing step (2), as described above, except that the order of lamination of each layer is limited in order to prepare the support sheet in advance, the film for forming the protective film, and the film for forming the protective film on the support sheet, the rest is the same as the manufacturing method ( The production step (1) of the laminated sheet in S1) is the same.

>>Protection step of supporting sheet, preservation step of protective film formation film>> The above support sheet storage step and protective film formation film storage step can be stored in the same way as the laminate in the manufacturing method (S1) except that the object to be stored is not a laminate sheet but a difference between the support sheet or the protective film formation membrane. The procedure is the same. At this time, for example, the storage time of the support sheet and the protective film forming film is the same as that of the laminated sheet, and it can be 24 to 720 hours (1 to 30 days), 48 to 480 hours (2 to 20 days), and 72 to 240 Any one of the hours (3~10 days).

On the other hand, the above-mentioned support sheet storage step and protective film formation film storage step are the same as the above-mentioned change of the storage object, and the storage time of the storage object (support sheet or protective film forming film) is further changed, among others Other than the change point, the rest can be carried out in the same manner as in the lamination sheet storage step in the manufacturing method (S1). At this time, for example, the storage time of the support sheet and the protective film forming film may be 12 to 720 hours (0.5 to 30 days), 12 to 480 hours (0.5 to 20 days), and 12 to 240 hours (0.5 to 10 days) ). However, this is only an example of the above storage time. [Example]

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

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

[Example 1] >Manufacture of support sheet> (Manufacture of adhesive composition (I-4)) Manufacturing a non-energy ray-curable adhesive composition (I-4) having a solid content concentration of 30% by mass, which contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate system A cross-linking agent ("TAKENATE D110N" manufactured by Mitsui Takeda Chemicals Co., Ltd.) (40 parts by mass (solid content)) as a solvent also contains a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate. The above acrylic polymer is a prepolymer obtained 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 800,000 Copolymer.

(Manufacture of support sheet) A peeling film (“SP-PET381031” manufactured by LINTEC Corporation, thickness 38 μm) was peeled off on one side of the film made of polyethylene terephthalate by silicone treatment, and coated on the above peeling treatment 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, the conditions were set so that the thickness of the adhesive layer became 4 μm, and the adhesive composition (I-4) was applied.

The surface of one side of the polypropylene film (made by Mitsubishi Resin Co., Ltd., thickness 80 μm) was made to rotate and pressurize the uneven surface of the metal roll while heating, and the surface on one side was made into an uneven surface, and the surface on the other side was Base material with smooth surface (smooth surface). The uneven surface of this substrate was 5 μm when the maximum height roughness (Rz) was measured according to JIS B 0601:2013.

Next, by bonding the uneven surface of the base material on the exposed surface of the adhesive layer obtained above, a support sheet formed by stacking the base material, the adhesive layer and the release film in this order in the thickness direction is obtained. The width of the obtained support sheet (in other words, the width of the base material and the adhesive layer) was 400 mm. With the above, the support sheet of the present invention is obtained.

Next, with respect to the support sheet, the following evaluation of the non-lamination area between the base material and the adhesive layer was immediately performed. In addition, this supporting sheet is used in the production of the composite sheet for forming a protective film described below.

>Manufacture of composite sheet for forming protective film> (Manufacture of composition (III-1) for forming a protective film) By combining the polymer component (A)-1 (150 parts by mass), the thermosetting component (B1)-1 (60 parts by mass), (B1)-2 (10 parts by mass), (B1)-3(30 Parts by mass), (B2)-1 (2 parts by mass), hardening accelerator (C)-1 (2 parts by mass), filler (D)-1 (320 parts by mass), coupling agent (E)-1( 2 parts by mass) and coloring agent (I)-1 (18 parts by mass) dissolved or dispersed in a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate, and stirred at 23°C to obtain a thermosetting property with a solid content concentration of 51% by mass The protective film forming composition (III-1). In addition, all the formulation amounts shown here are solid parts.

(Manufacture of protective film forming film) Use a peeling film (the second peeling film, "SP-PET381031" manufactured by LINTEC Co., Ltd., thickness 38 μm) on one side of the polyethylene terephthalate film that has been peeled off by silicone treatment on one side. The treated surface was peeled off, and the composition (III-1) for forming a protective film obtained above was applied using a knife coater and dried at 100° C. for 2 minutes to produce a thermosetting protective film with a thickness of 25 μm.用膜。 With membrane.

Furthermore, by peeling off the exposed surface of the obtained film for protective film formation which does not have the 2nd peeling film side, the peeling film (1st peeling film, "SP-PET381031" by LINTEC Corporation, thickness 38 micrometers) was bonded. On the surface, a laminated film including the first release film on the side of the protective film forming film and the second release film on the other side is obtained. The width of the obtained laminated film (in other words, the width of the protective film forming film, the width of the first release film and the second release film) was 400 mm.

(Manufacture of composite sheet for forming protective film) One set (two pieces) with a diameter of 5 cm and a depth from its inner surface to a depth of 3 mm was prepared as a roller made of heat-resistant silicone rubber with a hardness of 50 degrees. The release film is removed from the adhesive layer of the support sheet obtained above. In addition, the first release film is removed from the laminate film obtained above. Then, the exposed surface of the adhesive layer resulting from the removal of the peeling film is bonded to the exposed surface of the protective film forming film resulting from the removal of the first peeling film, and the support sheet and the protective film The film for forming is stacked to form a laminate, and by using this laminate at a speed of 0.3 m/min, through the gap between these rollers whose temperature is set at 60° C., it is heated and pressurized with a pressure of 0.5 MPa (heat Laminated). In this way, a laminate having the same layered structure as the target protective film-forming composite sheet formed by stacking the base material, the adhesive layer, the film for forming a protective film, and the second release film in this order is prepared. Sheet (composite sheet for forming a protective film before storage). In the obtained laminated sheet, the width (in other words, the width of the support sheet) was 400 mm, and the outer diameter of the protective film forming film was 330 mm.

Next, using the overall obtained laminate having a size of 400 mm × 50 m, with the longitudinal direction as the winding direction, the winding tension was 160 N/m, the winding speed was 50 m/min, and the winding tension was 90. Under the condition of %, the roll is attached to the core of ABS resin and wound into a roll shape. At this time, the base material is wound outward in the radial direction of the roller (in other words, the second release film is brought into contact with the core), and the laminate sheet is wound. Next, this roll-shaped laminated sheet was stored in an air environment at a temperature of 60° C. for 7 days (168 hours). Thereby, the composite sheet for forming a protective film of the present invention having the structure shown in FIG. 2 is obtained.

Next, with respect to the composite sheet for forming a protective film of the present invention after completion of storage under such heat and pressure conditions, the following items were evaluated.

>Evaluation of composite sheet for forming support sheet and protective film> (Measurement of the thickness of the adhesive layer) A test piece having a size of 3 mm × 3 mm was cut out from 5 places of the composite sheet for forming a protective film obtained above. The five cut-out positions are the one corresponding to the central part of the film for forming a round protective film, and the four parts corresponding to the positions that are substantially point-symmetrical with respect to the central part near the edge . Among these five cut-out positions, one corresponds to one center portion, and the center-to-center distance from the four outer portions near the edge portion is 100 mm.

Using a cross-section sample making device ("cross section polisher SM-09010" manufactured by JEOL), the conditions of the intermittent shutter are "in" for 10 seconds and "out" for 5 seconds, the ion source voltage is 3kV, and the total polishing time is 24 hours. A cross section is formed from the above test piece. In the newly formed section, only one side is formed on one test piece.

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

(Evaluation of the stackability of the adhesive layer and the protective film forming film) For the composite sheet for forming a protective film obtained above, light is irradiated from the outside of the base material side, is there a non-bonding area between the adhesive layer and the film for forming a protective film, and the supporting sheet is interposed from the outside of the base material side Confirm visually. At this time, it was visually confirmed that it was carried out across the entire formation area of the protective film forming film in the protective film forming composite sheet. Then, the degree of lamination between the adhesive layer and the film for forming a protective film was evaluated according to the following criteria. The results are shown in Table 1. A: There is no non-sticking area. B: Although there are non-laminated areas, the number is 3 or less. C: There are 4 or more non-laminated areas.

(Evaluation of the legibility of the protective film) From the obtained composite film for protective film formation, the second release film was removed, and the exposed surface (the surface opposite to the adhesive layer side) of the resulting protective film formation film was attached to an 8-inch semiconductor The back of the wafer. The attachment at this time was performed using a tape mounter ("RAD2700" manufactured by LINTEC Corporation). In this way, a first build-up structure in which the base material, the adhesive layer, the film for forming a protective film, and the semiconductor wafer are stacked in this order in the thickness direction is produced.

Next, using a laser printing device ("CSM300M" manufactured by EO Technics), the surface (second side) on the side of the adhesive layer of the protective film forming film in the first laminated structure was interposed by the support sheet Printing by irradiating laser light. At this time, characters with a size of 0.3 mm × 0.2 mm are printed.

Next, the printing (laser printing) of this protective film forming film was visually observed through the support sheet, and the legibility of the printing (character) was evaluated according to the following criteria. The results are shown in Table 1. The printability of the protective film forming film evaluated here is regarded as equivalent to the printability of the protective film. A: The printing is clear and can be easily recognized. B: The printing is a little vague and cannot be easily recognized. C: The printing is not clear and cannot be recognized.

Next, the supporting sheet (base material and adhesive layer) is peeled off from this protective film forming film. Then, using an optical microscope (manufactured by KEYENCE), the thickness of the line of the printing (letter) formed on the protective film forming film was measured. As a result, the thickness of the line is 40 μm or more, and the characters are clearly printed.

(Evaluate the presence or absence of non-bonding areas between the substrate and the adhesive layer and the distance between the layers) Using a scanning electron microscope (SEM, "VE-9700" manufactured by Keyence Corporation), the presence or absence of the non-lamination area between the base material and the adhesive layer was confirmed for the obtained protective film forming composite sheet. Then, when there is a non-laminated area, the distance between the layers is measured. The confirmation and measurement at this time are performed across the entire area of the base material and the adhesive layer. In addition, when measuring this interlayer distance, a cross-section is formed on the composite film for forming a protective film by the same method as in the case of the above-mentioned test piece, and on this cross-section, the interlayer distance between the base material and the adhesive layer is determined. Then, according to the following criteria, evaluation was performed on the non-laminated area between the base material and the adhesive layer. The results are shown in Table 1. A: There is no non-sticking area. B: Although there is a non-laminated area, the interlayer distance is 0.5 μm or less. C: There is a non-laminated area, and the interlayer distance is greater than 0.5 μm.

(Evaluate the presence or absence of non-bonding areas between the adhesive layer and the protective film forming film and the distance between the layers) When evaluating the non-bonding area between the base material and the adhesive layer, the presence or absence of the non-bonding area between the adhesive layer and the film for forming a protective film was also confirmed. Then, when there is a non-laminated area, the distance between the layers is measured. The confirmation and the measurement at this time were performed across the entire formation area of the protective film forming film in the protective film forming composite sheet. In addition, when measuring this interlayer distance, a cross section is formed on the composite film for forming a protective film by the same method as in the case of the above-mentioned test piece, and on this cross section, the interlayer distance between the adhesive layer and the film for forming a protective film is measured. Then, according to the following criteria, evaluation was performed on the non-laminated area between the adhesive layer and the film for forming a protective film. The results are shown in Table 1. A: There is no non-sticking area. B: Although there is a non-laminated area, the interlayer distance is 0.5 μm or less. C: There is a non-laminated area, and the interlayer distance is greater than 0.5 μm.

(Evaluation of the unevenness of the second surface of the protective film forming film) From the composite sheet for forming a protective film obtained above, the second release film is removed, and the exposed surface (the surface opposite to the adhesive layer side and the first surface) of the resulting film for forming a protective film is attached to The back surface of an 8-inch semiconductor wafer (200 μm thick). The attachment at this time was performed using a tape mounter ("RAD2700" manufactured by LINTEC Corporation). In this way, a first build-up structure in which the base material, the adhesive layer, the film for forming a protective film, and the semiconductor wafer are stacked in this order in the thickness direction is produced. Next, the state of the surface (second surface) on the adhesive layer side of the protective film forming film after the semiconductor wafer was attached was visually confirmed through the support sheet, and evaluated according to the following criteria. The results are shown in Table 1. The unevenness on the second surface of the protective film forming film evaluated here is regarded as equivalent to the unevenness on the surface (second surface) on the side opposite to the semiconductor wafer side of the protective film. A: The smoothness or the unevenness is extremely small, and the appearance of the protective film forming film is not impaired. B: There is unevenness in one part, and although the unevenness is extremely small, the unevenness is extremely small, and the appearance of the protective film forming film is not impaired. C: The unevenness is large, which impairs the appearance of the protective film forming film.

>Manufacture of composite sheet for forming support sheet and protective film and evaluation of composite sheet for forming support sheet and protective film> [Example 2] The support sheet was produced and evaluated by the same method as in Example 1 except that the thickness of the adhesive layer was not 4 μm but 5 μm to set the conditions and the difference between the application of the adhesive composition (I-4). . Then, except for the difference in using such a support sheet, a composite sheet for forming a protective film was produced and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Example 3] The support sheet was manufactured and evaluated in the same manner as in Example 1, except that the thickness of the adhesive layer was not 4 μm but 6 μm to set the conditions and the difference between the application of the adhesive composition (I-4). . Then, except for the difference in using such a support sheet, a composite sheet for forming a protective film was produced and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Comparative Example 1] The support sheet was produced and evaluated in the same manner as in Example 1, except that the thickness of the adhesive layer was not 4 μm but 3 μm, the conditions were set, and the difference between applying the adhesive composition (I-4) was used. . Then, except for the difference in using such a support sheet, a composite sheet for forming a protective film was produced and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Comparative Example 2] The surface of one side of the polypropylene film (made by Mitsubishi Resin Co., Ltd., thickness 80 μm) was heated and rotated with pressure while heating the uneven surface of the metal roll, making the surface on one side an uneven surface and the other side The surface is a substrate with a smooth surface (smooth surface). The unevenness of the metal roller used at this time is larger than the unevenness of the metal roller used in Example 1. The uneven surface of the obtained base material was 8 μm when the maximum height roughness (Rz) was measured according to JIS B 0601:2013.

Except for the difference between using the substrate obtained above and the thickness of the adhesive layer not to be 4 μm but to 7 μm, the conditions were set and the difference between applying the adhesive composition (I-4) was applied. In the same way, the support sheet was manufactured and evaluated. Then, except for the difference in using such a support sheet, a composite sheet for forming a protective film was produced and evaluated by the same method as in Example 1. The results are shown in Table 1.

[Table 1]

From the above results, it is clear that in Examples 1 to 3, the S value of the adhesive layer is 2 μm or more (2 to 4 μm), and the stackability of the adhesive layer and the film for forming a protective film is particularly good. In addition, in these embodiments, the L value of the adhesive layer is 8 μm or less (6 to 8 μm), and the printability of the protective film (film for forming a protective film) is particularly good.

On the other hand, in Comparative Example 1, the S value of the adhesive layer was 1 μm, because there was an extremely thin region in the adhesive layer. Therefore, there are a plurality of non-bonding regions between the adhesive layer and the film for forming a protective film, and the lamination property of the adhesive layer and the film for forming a protective film becomes poor. In addition, since there is such a non-lamination area, the legibility of the protective film (film for forming a protective film) across the support sheet also deteriorates.

Furthermore, in Comparative Example 2, the L value of the adhesive layer was 10 μm, and there was an extremely thick region in the adhesive layer. Therefore, the legibility of the protective film (the film for forming a protective film) across the support sheet deteriorates.

In addition, in Examples 1 to 3, there is no non-bonding area at all between the base material and the adhesive layer, or between the adhesive layer and the protective film forming film, or even if there is, the interlayer distance Very small, the composite sheet for forming a protective film has good characteristics. In addition, in Examples 1 to 3, the unevenness on the second surface of the protective film forming film is small, the protective film forming film has an excellent appearance, and a protective film with high design can be formed. [Industry availability]

The present invention can be applied to the manufacture of semiconductor devices.

1A, 1B, 1C‧‧‧‧Composite sheet for protective film formation 10‧‧‧Support sheet 10a‧‧‧Support film on the protective film formation membrane side surface (first surface) 10b‧‧‧Support sheet surface (first (Two sides) 11‧‧‧ base material 11a‧‧‧ base material adhesive layer side surface (first surface, uneven surface) 11b‧‧‧ base material opposite adhesive layer side surface (second surface) 12‧‧‧adhesive layer 12a‧‧‧adhesive layer surface opposite to the substrate side (first surface) 12b‧‧‧adhesive layer substrate side surface (second surface) 13,23‧ ‧‧Protective film forming film 13a‧‧‧Protective film forming film surface (first surface) 13b‧‧‧Protective film forming film adhesive layer side surface (second surface) 15‧‧‧Releasable film 16‧‧‧ Adhesive layer for jig 16a‧‧‧ (without contact with protective film forming film) surface 23a‧‧‧ (without contact with adhesive layer) surface 23b‧‧‧‧ Adhesive for protective film forming film Layer-side surface (second surface) 91 ‧‧‧ Unbonded area of the substrate and the adhesive layer (non-bonded area) 92 ‧‧‧ Unbonded area of the adhesive layer and protective film forming film (non-bonded Bonding area) Ta‧‧‧ Thickness of adhesive layer Ta1‧‧‧Minimum thickness of adhesive layer Ta2‧‧‧Maximum thickness of adhesive layer T _p ‧‧‧Thickness of protective film forming film

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

1A‧‧‧Composite sheet for forming protective film

10‧‧‧support sheet

10a‧‧‧The film side surface (first surface) for forming the protective film of the support sheet

10b‧‧‧The side of the support piece (second side)

11‧‧‧ Base material

11a‧‧‧The surface of the base material on the adhesive layer side (first surface, uneven surface)

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

12‧‧‧Adhesive layer

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

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

13‧‧‧Protective film forming film

13a‧‧‧Face of protective film (first side)

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

15‧‧‧ peeling film

16‧‧‧Adhesive layer for jigs

16a‧‧‧(without contact with the protective film forming film) surface

Claims (3)

A support sheet is a support sheet including a substrate and an adhesive layer on the substrate, The surface of the base material on the side of the adhesive layer is an uneven surface, Test pieces were cut out from the above five support pieces, and among these 5 test pieces, When the minimum value and the maximum value of the thickness of each adhesive layer are determined, the average value of the minimum value is 1.5 μm or more, and the average value of the maximum value is 9 μm or less. The support sheet according to item 1 of the patent application scope, wherein the adhesive layer directly contacts the uneven surface of the base material. A composite film for forming a protective film includes a film for forming a protective film on the adhesive layer of the support sheet as described in item 1 or 2 of the patent application.

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