TWI788543B - Supporting sheet and composite sheet for forming protective film - Google Patents

Abstract

A supporting sheet of the present invention includes a substrate and an adhesive layer on the substrate, wherein the surface of the adhesive layer side of the substrate is an even surface. When test pieces are cut from five locations on the supporting sheet and the cross-sections of the adhesive layers of the five test pieces are observed, the average ratio (R-value) of the total linear distance between adjacent significant peaks/the linear distance in the horizontal direction with respect to the adhesive layer is 1.5 or more and less than 5.0.

Description

Composite sheet for support sheet and protective film formation

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

In recent years, a semiconductor device has been manufactured by applying a packaging method of a so-called face down method. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on the circuit surface is used, and the electrodes are bonded to the substrate. Therefore, the back surface on the opposite side to the circuit surface of the semiconductor wafer may be exposed.

In some cases, a resin film containing an organic material is formed on the back surface of the exposed semiconductor wafer as a protective film, and it is incorporated into a semiconductor device as a semiconductor wafer with a protective film. The protective film is used to prevent cracks from occurring on the semiconductor wafer during the dicing process and after packaging.

Such a protective film can be formed, for example, by curing a curable thin film for forming a protective film. Moreover, the film for non-curable protective film formation whose physical property was adjusted can also be used as a protective film as it is. In addition, the thin film for protective film formation is used by sticking to the back surface of a semiconductor wafer. For example, there are cases where the film for forming a protective film is integrated with a support sheet used in processing a semiconductor wafer, and is attached to the back of the semiconductor wafer in the state of a composite sheet for forming a protective film. The state of being integrated with the support sheet, and the state of being attached to the back surface of the semiconductor wafer.

After the composite sheet for forming a protective film is attached to the back surface of the semiconductor wafer with the thin film for forming a protective film therein, the protective film is formed by hardening the thin film for forming a protective film by appropriate dicing, and the The film for forming a protective film or the protective film is cut and the semiconductor wafer is divided (diced) into a semiconductor wafer, and the semiconductor wafer (with protective film) having the thin film for forming a protective film or the protective film after cutting on the back surface is suitably processed Thin-film-forming semiconductor wafers or semiconductor wafers with protective films) are picked up from a support sheet, etc. When picking up a semiconductor wafer with a protective film forming film, it becomes a semiconductor wafer with a protective film by hardening the protective film forming film, and finally a semiconductor device can be manufactured using the semiconductor wafer with a protective film. Thus, the support sheet in the composite sheet for protective film formation can be utilized as a dicing sheet. Moreover, when the thin film for protective film formation is non-curable, in each of these steps, the thin film for protective film formation can be used as it is and handled as a protective film.

On the other hand, after 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 support sheet is attached to the semiconductor wafer after the protective film forming film is attached. The surface is the exposed surface of the opposite side. Thereafter, by using the same method as in the above-mentioned composite sheet for forming a protective film, a semiconductor wafer with a protective film or a semiconductor wafer with a thin film for forming a protective film can be obtained, and a semiconductor device can be manufactured. At this time, the thin film for protective film formation is attached to the back surface of the semiconductor wafer without being integrated with the support sheet, but the composite sheet for protective film formation is constituted by integrating with the support sheet after attachment.

As such a composite sheet for forming a protective film, for example, a dicing tape-integrated film for protecting the back surface of a semiconductor has been disclosed. Adhesive layer on the concave-convex processed surface side; and a film for semiconductor back protection (film for forming a protective film), a dicing tape-integrated semiconductor back protection film laminated on the adhesive layer of the dicing tape; fog of the aforementioned dicing tape The degree is 45% or less (see Patent Document 1).

However, in the composite sheet for forming a protective film disclosed in Patent Document 1 (dicing tape-integrated film for protecting the back surface of a semiconductor), the adhesive cannot sufficiently follow the substrate by laminating the adhesive on the uneven surface side of the substrate. unevenness, and these unbonded regions (non-bonded regions) are generated between the base material and the adhesive. Also, on the surface of the protective film or the film for forming a protective film on the side of the adhesive layer, printing may be performed by laser irradiation, but due to the irregular shape of the adhesive layer, the printing through the base material and the adhesive layer may not be possible. Visibility is reduced. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 5432853

The problem to be solved by the invention

The object of the present invention is to provide a support sheet and a composite sheet for forming a protective film provided with the above-mentioned support sheet. The protective film forming composite sheet of the protective film forming film can achieve good adhesion between the base material and the adhesive, and good printing visibility through the protective film or the support sheet of the protective film forming film. means to solve problems

The present invention provides a support sheet comprising a base material and an adhesive layer on the base material, wherein the surface of the base material on the side of the adhesive layer is a concave-convex surface, and is cut from 5 places of the support sheet for testing. When observing the cross-section of the aforementioned adhesive layer on these 5 test pieces, the average ratio of (the sum of the straight-line distances between adjacent meaningful vertices)/(the straight-line distance in the horizontal direction to the adhesive layer) The value is 1.5 or more and less than 5.0.

In the support sheet of the present invention, the aforementioned adhesive layer may also be in direct contact with the concave-convex surface of the aforementioned substrate. Moreover, this invention provides the composite sheet for protective film formation provided with the thin film for protective film formation on the adhesive agent layer in the said support sheet. Invention effect

By constituting the composite sheet for protective film formation using the support sheet of the present invention, good adhesion between the base material and the adhesive, and good visibility of printed characters through the support sheet through the protective film or the film for protective film formation can be achieved.

form for carrying out the invention

◇Composite sheet for support sheet and protective film formation A support sheet according to an embodiment of the present invention is a support sheet having 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. When the test pieces are cut and the cross-section of the aforementioned adhesive layer is observed on these 5 test pieces, the ratio of (total linear distances between adjacent meaningful vertices)/(straight-line distance in the horizontal direction to the adhesive layer) The average value (in this specification, there is a case called "R value") is 1.5 or more and less than 5.0.

Also, in this specification, when the cross section of the adhesive layer is observed, the surface of the adhesive layer on the substrate side changes from descending to rising at the top of the convex portion, and the surface of the adhesive layer on the substrate side changes from ascending to descending. When the step difference between the deepest parts of the concave part is 1 μm or more, the step difference is considered to be meaningful, and the aforementioned apex having the meaningful step difference is specified as a meaningful vertex of the convex part, and the aforementioned deepest part having the meaningful step difference Specific to the meaningful vertices of the concave part, among the meaningful vertices of the convex part and the meaningful vertices of the concave part, the distance between the adjacent meaningful vertices connected by a straight line is defined as "the distance between the adjacent meaningful vertices The straight-line distance between”, and the sum of the straight-line distances between adjacent meaningful vertices of the observation object is defined as the “total of the straight-line distances between adjacent meaningful vertices”. In addition, the distance from the start point to the end point of the projected meaningful vertex of the observation object to the point formed by the plane horizontal to the adhesive layer is defined as "straight-line distance horizontal to the adhesive layer".

When the cross section of the adhesive layer is observed, the average value (R value) of the ratio of (the sum of the linear distances between adjacent meaningful vertices)/(the linear distance in the horizontal direction to the adhesive layer) is 1.5 or more , Substrate and adhesive and adhesion become good. When the R value is less than 5.0, scattering of transmitted light at the adhesive-substrate interface can be suppressed, and good visibility of printed characters transmitted through the protective film or the support sheet of the film for protective film formation can be realized.

A support sheet according to an embodiment of the present invention is a support sheet having 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. Cut the test pieces, and when the minimum value and maximum value of the thickness of the adhesive layer are calculated for each of the five test pieces, it is preferable to be the average value of the above-mentioned minimum value (in this manual, there is a case called "S value") ) is 1.5 μm or more and the average value of the aforementioned maximum values (in this specification, sometimes referred to as “L value”) is 9 μm or less. Moreover, the composite sheet for protective film formation which concerns on one Embodiment of this invention is equipped with the thin film for protective film formation on the adhesive agent layer in the said support sheet.

Moreover, since the S value of the said adhesive layer is 1.5 micrometers or more, lamination|stackability of an adhesive layer and the film for protective film formation becomes favorable easily. In this specification, "lamination property" means the normality of the lamination state of the two layers of the object, unless otherwise specified. The so-called "good lamination" means that, for example, there is no non-bonding area (gap) between two adjacent layers of the object, or the number of non-bonding areas is small, and the interlayer distance of the non-bonding area is smaller. On the other hand, when the L value of the pressure-sensitive adhesive layer is 9 μm or less, the visibility of printed characters through the support sheet of the protective film or the film for forming a protective film tends to become good.

The aforementioned test piece was cut out from five places of the support sheet, and the support sheet was cut in the entire thickness direction thereof. The test piece is a fine piece having all the layers constituting the support piece.

The size of the test piece is not particularly limited, and the length of one side of the laminated surface or the exposed surface of each layer (substrate, adhesive layer, etc.) constituting the test piece is preferably 2 mm or more. By using a test piece of such a size, the R value, the S value, and the L value of the adhesive layer can be calculated|required more accurately. The maximum value of the length of one side is not particularly limited. For example, the length of one side is preferably 10 mm or less from the viewpoint of easier production of the test piece.

The planar shape of the test piece, that is, the shape of the laminated surface or the exposed surface of each layer (substrate, adhesive layer, etc.) constituting the test piece, is preferably a polygonal shape. A square shape is preferred.

As a preferable test piece, for example, a laminated layer or an exposed surface of each layer (substrate, adhesive layer, etc.) constituting the test piece has a quadrangular shape of 3 mm×3 mm. But this is an example of a better test piece.

The cutting positions of the five test pieces of the support sheet are not particularly limited, and the R value, S value, and L value of the adhesive layer can be obtained with higher accuracy, taking into account the planned layering of the film for protective film formation described later. selected by location. For example, among the positions where one film for forming a protective film is to be stacked on the support sheet, one of the centers (centers of gravity) of the film for forming a protective film is planned to be arranged; The peripheral part, and the 4 places that are roughly point-symmetrical to the central (center of gravity) part; a total of 5 places.

On the support piece, the distance between the cutting position of the test piece and the center (center of gravity) is preferably 50~200mm. Thereby, the R value, the S value, and the L value of an adhesive layer can be calculated|required more accurately.

In order to obtain the R value of the adhesive layer from the test piece, a new cross-section is formed on the test piece. In the formed cross-section, each test piece measures the sum of the linear distances between adjacent meaningful vertices, and the value of the adhesive layer. The level is the linear distance in the horizontal direction. For the newly formed section, each test piece may have only one side or more than two sides, and usually only one side is sufficient. Furthermore, the R value may be calculated from the sum of the linear distances between the at least five adjacent meaningful vertices and the linear distance in the horizontal direction with respect to the adhesive layer.

In order to obtain the S value and L value of the adhesive layer from the test piece, a cross section was newly formed on the test piece, and the minimum value and the maximum value of the thickness of the adhesive layer were measured for each test piece on the formed cross section. For the newly formed section, each test piece may have only one side or more than two sides, and usually only one side is sufficient. And it is sufficient that the S value and the L value can be calculated from these at least five minimum values and maximum values.

The cross section of the test piece can be formed by a known method. For example, by using a known cross-section sample manufacturing device (cross-section polisher), it is possible to form a cross-section on a test piece with high reproducibility while suppressing variations.

The sum of the straight-line distances between adjacent significant vertices of the adhesive layer, and the straight-line distance in the horizontal direction to the adhesive layer, for example, can be imaged by using a scanning electron microscope (SEM) to image the aforementioned cross-section of the test piece processing to measure. The minimum value and maximum value of the thickness of an adhesive layer can be measured, for example by observing the said cross-section of a test piece using a scanning electron microscope (SEM).

On the aforementioned cross-section of each test piece, measure the sum of the linear distances between adjacent meaningful vertices and the area of the linear distance in the horizontal direction to the adhesive layer, preferably for each layer (substrate, substrate, etc.) constituting the test piece The lamination direction of the adhesive layer, etc.) is a region of 50 to 1500 μm in the orthogonal direction (direction approximately parallel to the lamination layer or exposed surface of each layer). Moreover, when cutting out the test piece from the elongate support sheet and the composite sheet for protective film formation, it is preferable to cut the said cross-section in the width direction of the elongate support sheet and the composite sheet for protective film formation. Thereby, the total of the linear distances between adjacent significant vertices and the linear distance in the horizontal direction with respect to the adhesive layer can be measured efficiently and with high accuracy. The same applies to the determination of the minimum and maximum values of the thickness of the adhesive layer. In addition, the calculation of the R value is not a fixed value as "the sum of the straight-line distances between adjacent meaningful vertices" and how many sets of meaningful vertices exist between the observation regions of the cross section of the test piece. For example, when the observation area of the cross-section of the test piece is set to an area of 1 mm, there may be 50 to 500 sets of meaningful vertices, 75 to 250 sets, or 100 to 200 sets of each other.

Between the support sheet at the stage where the composite sheet for protective film formation is not formed and the support sheet that constitutes the composite sheet for protective film formation, a test piece is cut out and the surface of the adhesive layer on the base material side (adjacent meaningful When comparing the average value (R value) of the ratio (the sum of the straight-line distances between vertices)/(the straight-line distance in the horizontal direction to the adhesive layer), these R values are the same as each other, or when the protective The said R value of the support sheet of the composite sheet for film formation becomes a little small, and even if it becomes small, the difference is negligible.

When comparing the minimum values of the thickness of the adhesive layer between the support sheet at the stage not constituting the composite sheet for forming a protective film and the support sheet constituting the composite sheet for forming a protective film, the minimum values are the same , or the above-mentioned minimum value of the support sheet constituting the composite sheet for protective film formation is slightly smaller, and even if it is smaller, the difference is negligible. The same applies to the maximum value of the thickness of the adhesive layer. That is, when the maximum value of the thickness of the adhesive layer is compared between the support sheet at the stage not constituting the composite sheet for forming a protective film and the support sheet constituting the composite sheet for forming a protective film, the maximum value They are the same as each other, or the above-mentioned maximum value of the support sheet constituting the composite sheet for protective film formation is slightly smaller, and even if it is smaller, the difference is negligible. Therefore, instead of the support sheet, a test piece cut out from the protective film forming composite sheet may be used, and the R value, the S value and the L value of the adhesive layer may be obtained using the same method as when the test piece is cut from the support sheet. value. When the test piece cut out from the composite sheet for protective film formation is used in this way, when the R value is 1.5 or more and less than 5.0, the composite sheet for protective film formation can reflect the effect of this invention mentioned above.

That is, a composite sheet for forming a protective film according to an embodiment of the present invention is a composite sheet for forming a protective film provided with a thin film for forming a protective film on the adhesive layer of the support sheet. Cut the test pieces at 5 locations, and observe the cross-section of the adhesive layer on these 5 test pieces, (the sum of the straight-line distances between adjacent meaningful vertices)/(the straight-line distance in the horizontal direction of the adhesive layer ) ratio (R value) is 1.5 or more and less than 5.0.

Similarly, instead of the support sheet at the stage that does not constitute the composite sheet for protective film formation, a test piece cut from the composite sheet for protective film formation can also be used, and by the same method as when using a test piece cut from the support sheet, the The S value and L value of the adhesive layer. When using the test piece cut out from the composite sheet for protective film formation in this way, 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 sheet for protective film formation is likely to reflect the above-mentioned principle. The effect of the invention.

That is, the composite sheet for forming a protective film according to an embodiment of the present invention is a composite sheet for forming a protective film provided with a thin film for forming a protective film on the adhesive layer of the support sheet. The test pieces are cut at 5 places, and when the minimum value and the maximum value of the thickness of the adhesive layer are obtained for each of the 5 test pieces, it is preferable that the average value (S value) of the above-mentioned minimum value is 1.5 μm or more, and the above-mentioned The average value (L value) of the maximum value is 9 μm or less.

In addition, the test piece cut out from the composite sheet for protective film formation is obtained by cutting the composite sheet for protective film formation in its entire thickness direction, and has fine pieces constituting all layers of the composite sheet for protective film formation. .

Hereinafter, the overall structure of the composite sheet for protective film formation of this invention is demonstrated, referring drawings. In addition, in the drawings used in the following description, in order to easily understand the characteristics of the present invention, important parts may be enlarged and displayed, and the dimensional ratio of each component is not limited to be the same as the actual one.

Fig. 1 schematically shows a cross-sectional view of a support sheet and a composite sheet for forming a protective film according to an embodiment of the present invention. The composite sheet 1A for protective film formation shown here is provided with the base material 11, and the adhesive agent layer 12 is provided on the base material 11, and the film 13 for protective film formation is provided on the adhesive agent layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, and the composite sheet 1A for forming a protective film, in other words, has one side (in this specification, sometimes referred to as "the first side") 10a on the support sheet 10 The upper buildup layer has a film 13 for forming a protective film. Moreover, 1 A of composite sheets for protective film formation are equipped with the peeling film 15 on the film 13 for protective film formation further.

In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one side (in this specification, sometimes referred to as "the first side") 11a of the base material 11, and on the side of the adhesive layer 12 and the base material 11 The film 13 for forming a protective film is layered on the entire surface of the surface (in this specification, sometimes referred to as "the first surface") 12a on the opposite side, and the film 13 for forming a protective film is on the side opposite to the side of the adhesive layer 12. (In this specification, it may be referred to as "the first surface") 13a, that is, the area near the peripheral part is laminated with the jig adhesive layer 16, and on the first surface of the protective film forming film 13 The peeling film 15 is laminated on the surface of 13a on which the adhesive layer 16 for jigs is not laminated, and 16a (top and side surfaces) of the adhesive layer 16 for jigs that is not in contact with the film 13 for forming a protective film. Moreover, in FIG. 1, the code|symbol 13b has shown the surface (in this specification, it may be called a "2nd surface" the case of the adhesive agent layer 12 side of the film 13 for protective film formation).

The adhesive layer 16 for jigs may have, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which layers containing an adhesive component are layered on both sides of the core sheet.

In 1A of composite sheets for protective film formation, the 1st surface 11a of the base material 11 is an uneven|corrugated surface. Moreover, the adhesive layer 12 is provided so that it may directly contact the 1st surface (concave-convex surface) 11a of the base material 11. As shown in FIG. Therefore, the surface 12b of the adhesive layer 12 on the side of the base material 11 (in this specification, it may be referred to as a "second surface") 12b is a concave-convex surface.

In the composite sheet 1A for forming a protective film, the surface 11b of the substrate 11 opposite to the side of the adhesive layer 12 (in this specification, sometimes referred to as "the second surface") 11b may be a concave-convex surface and a smooth surface (not uneven surface, glossy surface), preferably a smooth surface. The 2nd surface 11b of the base material 11 can also be said to be the surface (it may be called "2nd surface" in this specification) 10b of the support sheet 10 on the side opposite to the protective film forming film 13 side. The "uneven surface" and "smooth surface" will be described in detail later.

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

Fig. 2 schematically shows a cross-sectional view of a composite sheet for forming a protective film and a support sheet according to an embodiment of the present invention. In addition, in the figures after the 2nd figure, the thing shown in the illustration which has already been explained is the same component element, and the same code|symbol as the said illustration which has been explained is given, and the detailed description is abbreviate|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 it does not include the adhesive layer 16 for jigs. That is, in the protective film forming composite sheet 1B, the adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film forming film 13 is laminated on the entire first surface 12a of the adhesive layer 12, and The peeling film 15 is laminated|stacked on the whole area of the 1st surface 13a of the film 13 for protective film formation.

In the composite sheet 1B for protective film formation, the 1st surface 11a of the base material 11 is an uneven|corrugated surface. Moreover, the adhesive layer 12 is provided so that it may directly contact the 1st surface (concave-convex surface) 11a of the base material 11. As shown in FIG. 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) is also any one of a rough surface and a smooth surface (non-rough surface). good.

In the composite sheet 1B for forming a protective film shown in FIG. 2, the back surface of a semiconductor wafer (not shown) is attached to the first surface 13a of the film 13 for forming a protective film in a state where the release film 15 has been removed. Part of the central area and the area near the peripheral edge are attached to a jig such as a ring frame and used.

Fig. 3 also schematically shows a cross-sectional view of a composite sheet for forming a protective film and a support sheet according to another embodiment of the present invention. The protective film-forming composite sheet 1C shown here is the same as the protective film-forming composite sheet 1B shown in FIG. 2 except that the shape of the protective film-forming film is different. That is, 1 C of composite sheets for protective film formation are provided with the base material 11, the adhesive agent layer 12 is provided on the base material 11, and the film 23 for protective film formation is provided on the adhesive agent layer 12. The support sheet 10 is a laminated body of the base material 11 and the adhesive layer 12, and the composite sheet 1C for forming a protective film, in other words, has a first surface on which the film 23 for forming a protective film is laminated on the support sheet 10 (on the side of the film 23 for forming a protective film). The composition on the face) 10a. Moreover, 1 C of composite sheets for protective film formation are equipped with the peeling film 15 on the film 23 for protective film formation further.

In the protective film forming composite sheet 1C, the adhesive layer 12 is laminated on the first surface 11a of the base material 11, and the protective film forming film 23 is laminated on a part of the first surface 12a of the adhesive layer 12, that is, the center. side area. In addition, between the first surface 12a of the adhesive layer 12 where the film 23 for forming a protective film is not laminated, and the surface 23a (upper surface and side surfaces) of the film 23 for forming a protective film that is not in contact with the adhesive layer 12 Above, a release film 15 is laminated. Moreover, in FIG. 3, the code|symbol 23b has shown the surface by the side of the adhesive agent layer 12 of the film 23 for protective film formation (in this specification, it may call it a "2nd surface").

When the composite sheet 1C for protective film formation is planarly viewed from above, the thin film 23 for protective film formation is small compared with the surface area of the adhesive agent layer 12, and has shapes, such as a circle shape, for example.

In 1C of composite sheets for protective film formation, the 1st surface 11a of the base material 11 is an uneven|corrugated surface. Moreover, the adhesive layer 12 is provided so that it may directly contact the 1st surface (concave-convex surface) 11a of the base material 11. As shown in FIG. Therefore, the surface (2nd surface) 12b by the side of the base material 11 of the adhesive layer 12 is an uneven|corrugated surface. In the composite sheet 1C for forming a protective film, the second surface 11b of the substrate 11 (in other words, the second surface 10b of the support sheet 10) is either a concave-convex surface or a smooth surface (non-concave-convex surface). better.

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

Also, the composite sheet 1C for forming a protective film shown in FIG. 3 is an area where the film 23 for forming a protective film is not laminated on the first surface 12a of the adhesive layer 12, and may be the same as that shown in FIG. 1. The adhesive layer (not shown) for jigs is laminated|stacked similarly. Such a composite sheet 1C for forming a protective film having an adhesive layer for a jig can be attached to a ring frame or the like on the upper surface of the adhesive layer for a jig in the same way as the composite sheet for forming a protective film shown in FIG. 1 . Fixtures are used.

In this way, regardless of the form of the support sheet and the thin film for protective film formation, the composite sheet for protective film formation may be equipped with the adhesive layer for jigs. However, as shown in FIG. 1 , as the composite sheet for forming a protective film provided with an adhesive layer for a jig, it is preferable to have an adhesive layer for a jig on a film for forming a protective film.

The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to what is shown in FIGS. 1 to 3, and may be shown in FIGS. A part of the configuration of the thing is changed or removed, and a thing that is further added to the thing that has been described so far.

For example, in the composite sheet for forming a protective film shown in FIGS. 1 to 3 , an intermediate layer may be provided between the base material 11 and the adhesive layer 12 . That is, in the composite sheet for protective film formation of this invention, a support sheet may be comprised by laminating|stacking a base material, an intermediate layer, and an adhesive layer in this order in the thickness direction of these. As the intermediate layer, any one can be selected according to the purpose. Moreover, the composite sheet for protective film formation shown in FIG. 1 - FIG. 3 may be provided with the layer other than the said intermediate layer in arbitrary places. Furthermore, in the composite sheet for protective film formation, some gaps may be generated between the release film and the layer directly in contact with the release film. Furthermore, in the composite sheet for protective film formation, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

However, as shown in Figures 1 to 3, in the composite sheet for forming a protective film, it is preferable that the adhesive layer is the uneven surface (first surface) that directly contacts the base material, in other words, between the base material and the adhesive layer. Between, without an intermediate layer, and the adhesive layer is in direct contact and laminated on the substrate. In addition, in the composite sheet for forming a protective film, it is preferable that the film for forming a protective film is the first surface that directly contacts the adhesive layer, in other words, no other layer is provided between the adhesive layer and the film for forming a protective film, and the protective film is protected. The thin film for film formation is laminated|stacked on the adhesive agent layer for direct contact. Furthermore, the composite sheet for forming a protective film is more preferably one that satisfies all the conditions, that is, the base material, the adhesive layer, and the film for forming a protective film are laminated in this order in the thickness direction and directly contact each other. things.

The aforementioned supporting sheet is preferably transparent. The support sheet can be optionally colored and can also be vapor-deposited with other layers. For example, when the film for forming a protective film is energy ray curable, it is preferable that the support sheet can transmit energy ray.

In the present specification, the term "energy ray" means something having energy quanta among electromagnetic waves or charged particle rays, and examples thereof include ultraviolet rays, radiation rays, electron rays, and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet light source. Electron beams can be generated by electron beam accelerators and the like. In this specification, "energy ray curability" means the property of being cured by irradiation of energy ray, and "non-energy ray curability" means the property of not being cured even when irradiated with energy ray.

The light transmittance of the support sheet at a wavelength of 375nm is preferably above 30%, preferably above 50%, and especially preferably above 70%. When the transmittance of the said light is such a range, when the film for protective film formation is irradiated with energy rays (ultraviolet rays) through a support sheet, the degree of hardening of the thin film for protective film formation will be further improved. The upper limit of the transmittance of the support sheet to light with a wavelength of 375 nm is not particularly limited. For example, the light transmittance may be 95% or less.

The light transmittance of the support sheet at a wavelength of 532nm is preferably above 30%, preferably above 50%, and especially preferably above 70%. When the light transmittance is in such a range, when printing is performed by irradiating the protective film forming film or the protective film with laser light through the support sheet, it is possible to print more clearly. The upper limit of the transmittance of the support sheet to light with a wavelength of 532 nm is not particularly limited. For example, the light transmittance may be 95% or less.

The light transmittance of the support sheet at a wavelength of 1064nm is preferably above 30%, preferably above 50%, and especially preferably above 70%. When the light transmittance is in such a range, when printing is performed by irradiating the protective film forming film or the protective film with laser light through the support sheet, it is possible to print more clearly. The upper limit of the transmittance of the support sheet to light with a wavelength of 1064 nm is not particularly limited. For example, the light transmittance may be 95% or less.

The transparency of the support sheet is preferably 30 or higher, more preferably 100 or higher, and particularly preferably 200 or higher. When the above-mentioned transmission sharpness is in such a range, it is easier to confirm the floating and peeling of the film for forming a protective film, poor printing, chipping, etc. through the support sheet. The transparency of the support sheet is not particularly limited. For example, the aforementioned transmission clarity may be 430 or less. The transparency of the support sheet can be measured in accordance with JIS K7374-2007.

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

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

In this specification, the "uneven surface" means a surface with a maximum height roughness Rz of 0.01 μm or more according to JIS B0601:2013. In addition, the term "smooth surface" means a surface with a high degree of smoothness rather than an uneven surface, and may be called a "non-uneven surface" or a "glossy surface". For example, a smooth surface includes a surface with extremely small unevenness to such a degree that it does not correspond to the above-mentioned uneven surface.

In the substrate, only one side may be concave-convex, or both sides may be concave-convex, and only one side is preferably concave-convex. In other words, it is preferable that only one side of the substrate is smooth. In the support sheet, the concave-convex surface of the base material becomes the surface on the side provided with the adhesive layer.

The base material may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers. When composed of multiple layers, the multiple layers may be the same as or different from each other. The combination of layers is not particularly limited. When the base material is composed of multiple layers, the surface of the outermost layer among the multiple layers (the surface closest to the adhesive layer, or both sides of the surface closest to the adhesive layer and the farthest surface) becomes the aforementioned concave-convex surface .

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

On the concave-convex surface (first surface) on the side having the adhesive layer of the substrate, the R value of the substrate is preferably 1.3 or more and less than 4.8. It is preferably 1.5 or more, more preferably 1.7 or more, for example, it may be any one of 2.1 or more, 2.5 or more, 2.8 or more, and 3.3 or more. When the R value of the said base material is more than the said lower limit, the R value of an adhesive agent can be adjusted favorably. Here, the so-called R value of the base material means that test pieces are cut from 5 places of the base material, and when the cross-section of the aforementioned base material is observed on these 5 test pieces, (the linear distance between adjacent meaningful vertices The average value of the ratio of total)/(straight-line distance in the horizontal direction to the substrate).

In addition, the maximum height roughness (Rz) measured in accordance with JIS B0601:2013 on the concave-convex surface (first surface) on the side with the adhesive layer of the base material is preferably 0.01~8μm, more preferably 0.1~7μm , preferably 0.5~6μm. When said Rz of a base material is more than the said lower limit value, the defect which arises when a base material is individually wound up into a roll shape, or is unwound can be suppressed. In addition, in the production process of the support sheet or the composite sheet for protective film formation, it is also possible to suppress defects occurring at the time of winding up and unwinding of the laminate including the base material. On the other hand, when the Rz of the base material is not more than the above upper limit, the laminarity of the adhesive layer and the film for forming a protective film, and the visibility of the printed characters through the support sheet of the protective film or the film for forming a protective film are all changed. for good.

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

As a constituent material of the said base material, various resins are mentioned, for example. Examples of the aforementioned resin include polyethylene such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polypropylene, polybutene, 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- Ethylene-based copolymers such as norbornene copolymers (that is, copolymers obtained by using ethylene as a monomer); chlorinated vinyl resins such as polyvinyl chloride and vinyl chloride copolymers (that is, copolymers obtained by using vinyl chloride as a monomer obtained resin); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene Polyesters such as ethylene-2,6-naphthalene dicarboxylates and wholly aromatic polyesters whose structural units are aromatic ring groups; copolymers of two or more of the aforementioned polyesters; poly(methyl) Acrylic ester; polyurethane; polyurethane acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; . Moreover, as said resin, the polymer blend (polymer alloy) of the mixture of the said polyester and these other resins etc. is also mentioned, for example. The above-mentioned polymer blend of polyester and other resins is preferably one in which the amount of resins other than polyester is relatively small. Furthermore, as the above-mentioned resin, for example, a cross-linked resin obtained by cross-linking one or two or more of the above-mentioned resins exemplified so far; Modified resins such as ionic polymers.

In this specification, "(meth)acrylic acid" is used as a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid. For example, the so-called "(meth)acryl" includes the concepts of both "acryl" and "methacryl", and the so-called "(meth)acrylate" includes "acrylate" and "methacryl". The concept of both sides of acrylate.

The resin constituting the base material may be only one kind or two or more kinds, and when there are two or more kinds, the combinations and ratios thereof can be selected arbitrarily.

The thickness of the substrate is preferably within a range of 50 to 300 μm, more preferably within a range of 60 to 150 μm. When the thickness of the base material falls 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 substrate has uneven surfaces as described above, its thickness varies depending on the location of the substrate. Therefore, the minimum value of the thickness of a base material may be more than the said lower limit, and the maximum value of the thickness of a base material may be below the said upper limit. Also, the "thickness of the substrate" means the thickness of the entire substrate, for example, the thickness of a substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate.

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

For example, similar to the method described above, a test piece is cut out from multiple places (for example, 5 places) of the composite sheet for forming a support sheet or a protective film, and the minimum value and maximum value of the thickness of the base material are obtained on the test piece, Furthermore, when calculating the average value of the minimum value and the average value of the maximum value from these equivalent values, the average value of the above-mentioned minimum value may be more than the lower limit value of the above-mentioned substrate thickness, and the average value of the above-mentioned maximum value may be It is not more than the upper limit value of the said base material thickness.

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

The substrate is preferably transparent. The substrate can also be colored according to the purpose, and other layers can also be evaporated. For example, when the thin film for protective film formation is energy ray curable, it is preferable that the base material transmits energy ray.

In order to improve the adhesiveness of the layer directly in contact with the adhesive layer etc. provided thereon, the substrate may be subjected to corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone‧ultraviolet irradiation treatment, Oxidation treatment such as flame treatment, chromic acid treatment, hot air treatment, etc. In addition, the base material may be a surface treated with a primer. In addition, when the substrate is stored with an antistatic coating layer or a composite sheet for forming a protective film, it may also have a layer to prevent the substrate from being attached to another sheet or the substrate to be attached to an adsorption machine.

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

When using a substrate having no uneven surface (in other words, a substrate having smooth surfaces on both sides), the smooth surface of the substrate is subjected to a roughening treatment. The roughening process can be performed using a known method. For example, the smooth surface of the substrate can be roughened by using a metal roll or metal plate having a concave-convex surface and pressing the concave-convex surface against the smooth surface of the substrate. At this time, it is preferable to press the heated metal roll or metal plate against the smooth surface of the substrate.

For example, in addition to being able to use metal rolls with different concavities and convexities to produce substrates with desired concavo-convex surfaces, using metal rollers with the same concavities and convexities can be achieved by changing the temperature of the metal rollers or making the gap between the metal rollers By changing and changing the pressing pressure, it is also possible to manufacture a base material with the required concave-convex surface. In addition, the smooth surface of the base material can also be roughened by sandblasting, solvent treatment, or the like. The effect of the present invention will not be affected by using any method to produce the concave-convex object.

○Adhesive layer The aforementioned adhesive layer is in the form of a sheet or a film. In the adhesive layer, generally, regardless of the presence or absence of an intermediate layer between the base material and the adhesive layer, at least the surface on the base material side becomes an uneven surface due to the influence of the aforementioned uneven surface of the base material.

The adhesive layer may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers. When composed of multiple layers, the multiple layers may be the same as or different from each other. The combination of these plural layers is not particularly limited. When the adhesive layer is composed of plural layers, the surface of the outermost layer (the surface closest to the base material) among the plural layers becomes the above-mentioned concave-convex surface.

Here, the base material and the adhesive layer will be described in more detail with reference to the drawings. Fig. 4 schematically shows an enlarged cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. Here, the composite sheet 1A for protective film formation shown in FIG. 1 is taken as an example and demonstrated. In addition, illustration of the release film is omitted in FIG. 4 .

As described above, the first surface 11a of the substrate 11 is a concave-convex surface. Furthermore, the adhesive layer 12 is provided in direct contact with the first surface (concave-convex surface) 11 a of the substrate 11 , and the second surface 12 b of the adhesive layer 12 easily follows the first surface 11 a of the substrate 11 . Therefore, the second surface 12b of the adhesive layer 12 also becomes an uneven surface.

The straight-line distance between adjacent meaningful vertices is not constant, but varies according to the location of the adhesive layer 12 . Here, the straight-line distances between adjacent meaningful vertices are represented by symbols L _a1 , L _b1 , L _a2 , L _b2 . . . Also, among the line segments represented by symbols L _a1 , L _b1 , L _a2 , L _b2 ..., the line segment formed by projecting the line segments represented by symbols L _a1 and L _b1 onto a plane in which the adhesive layer is horizontal is represented by L ₁ , The line segment formed by projecting the line segments represented by symbols L _a2 and L _b2 on a plane in which the adhesive layer is horizontal is represented by L ₂ .

In the composite sheet 1A for forming a protective film, test pieces were cut out from five places thereof, and cross sections were formed on the five test pieces, and in the newly formed cross sections, the distance between all adjacent meaningful vertices of the adhesive layer was obtained. The linear distance between them (the above symbols L _a1 , L _b1 , L _a2 , L _b2 ...) and the linear distance between them are horizontal to the adhesive layer. Then, (the straight-line distance between all adjacent meaningful vertices (the sum of the above symbols L _a1 , L _b1 , L _a2 , L _b2 ...))/(the straight-line distance in the horizontal direction with respect to the adhesive layer (the above-mentioned symbol The ratio of the total length of the line segment represented by L ₁ , L ₂ ...)) is 1.5 or more and less than 5.0 when the average value (the aforementioned R value) is calculated from the values of at least 5 ratios.

Fig. 5 schematically shows an enlarged cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. Here, the composite sheet 1A for protective film formation shown in FIG. 1 is taken as an example and demonstrated. In addition, illustration of the release film is omitted in FIG. 5 .

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

In the composite sheet 1A for forming a protective film, test pieces are cut out from five places thereof, and cross-sections are formed on the five test pieces, and the minimum value T _a1 and the maximum thickness of the adhesive layer are obtained for each of the newly formed cross-sections. Value T _a2 . Furthermore, when calculating the average value (the aforementioned S value) from at least five T _a1 values, it is preferably 1.5 μm or more, and when calculating the average value (the aforementioned L value) from at least five T _a2 values , preferably below 9 μm.

Cut out a test piece from the composite sheet 1A for forming a protective film, form a section of the test piece, measure the R value of the adhesive layer on the aforementioned section, and measure the minimum value T _a1 and maximum value T _a2 of the thickness of the adhesive layer, As described above, it can be performed in the same manner as when the test piece is cut out from the support sheet constituting the composite sheet for protective film formation.

In addition, the enlarged cross-sectional view of the support sheet not constituting the composite sheet for forming a protective film is the same as that in which the film 13 for forming a protective film is omitted in FIGS. 4 and 5 .

As the composite sheet 1A for forming a protective film, it is shown here that such unbonded regions exist between the base material 11 and the adhesive layer 12 (in this specification, they may be referred to as "non-bonded regions"). 91. However, even if the protective film forming composite sheet 1A has such a non-bonding region 91, the size of the non-bonding region 91 in the thickness direction of the protective film forming composite sheet 1A is, for example, 0.5 μm or less in the protective film forming composite sheet 1A. , the lamination property of the base material 11 and the adhesive layer 12 is good, and it can be said to have good characteristics.

In addition, in this specification, "the size of the non-bonding area in the thickness direction of the composite sheet for protective film formation" means "the interlayer distance between the two adjacent sheets of the composite sheet for protective film formation in the thickness direction ", and there is a situation called "distance between layers" for short. For example, "the size of the non-bonding region 91 in the thickness direction of the protective film forming composite sheet 1A" mentioned above means "the interlayer distance between the base material 11 and the adhesive layer 12 in the thickness direction of the sheet 1A." . When the size (distance between layers) of the non-bonding area at one point fluctuates, the maximum value is adopted as the size (distance between layers) of the non-bonding area.

The size (distance between layers) of the non-bonding region can be measured, for example, using the same method as in the case of the above-mentioned R value of the adhesive layer. That is, a cross section can be formed on the test piece of the composite sheet for protective film formation using the same method as when calculating the R value of the adhesive layer, and the size of the non-bonding region can be obtained on the cross section. Alternatively, without producing a test piece, a cross section may be formed on the protective film forming composite sheet itself, and the size of the non-bonding region may be determined on the cross section.

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

In 1A of composite sheets for protective film formation, the non-bonding area|region 91 may not exist at all. In this specification, when there is no non-bonding region 91 at all, the size (distance between layers) of the non-bonding region 91 may be described as 0 μm.

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

The R value of the adhesive layer is not particularly limited as long as it is 1.5 or more and less than 5.0. It is preferably 1.7 or more, more preferably 1.9 or more, for example, it may be any value of 2.3 or more, 2.7 or more, 3.1 or more, and 3.5 or more. one. When the said R value is more than the said lower limit, the adhesiveness of a base material and an adhesive becomes more favorable.

On the other hand, the R value of the adhesive layer may be, for example, 4.5 or less, or may be 4.0 or less. Such an adhesive layer is a protective film or a film for forming a protective film, and the visibility of printed characters through the support sheet becomes good.

The R value of the adhesive layer can be appropriately adjusted within the set range by arbitrarily combining the above-mentioned preferable lower limit and upper limit. For example, the R value of the adhesive layer is preferably 1.5~4, preferably 1.7~4, more preferably 1.9~4, for example, any one of 2.3~4, 2.7~4, 3.1~4, and 3.5~4 . But this is an example of the R value of the adhesive layer.

The S value of the adhesive layer is not particularly limited unless the effects of the present invention are impaired, but is preferably 1.5 μm or more and less than 9 μm. It is preferably 1.7 μm or more, and is particularly preferably 1.9 μm or more. For example, it may be any of 2.3 μm or more, 2.7 μm or more, 3.1 μm or more, and 3.5 μm or more. When the said S value is more than the said lower limit, the laminarity of an adhesive layer and the film for protective film formation becomes more favorable.

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 appropriately adjusted within the set range by arbitrarily combining the above-mentioned preferable lower limit value and upper limit value. For example, the S value of the adhesive layer is preferably 1.5-8 μm, preferably 1.7-8 μm, more preferably 1.9-8 μm, for example, any of 2.3-8 μm, 2.7-8 μm, 3.1-8 μm, and 3.5-8 μm . 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 the effect of the present invention is not impaired, but it is preferably 9 μm or less and greater than 1.5 μm. It is preferably 8.6 μm or less, particularly preferably 8.3 μm or less, for example, it may be any of 7.7 μm or less, 7.3 μm or less, 6.9 μm or less, and 6.5 μm or less. When the said L value is below the said upper limit, the visibility of the printed characters through a support sheet of a protective film or the film for protective film formation becomes more favorable.

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

The L value of the adhesive layer can be appropriately adjusted within the set range by arbitrarily combining the above-mentioned preferable lower limit value and upper limit value. For example, the L value of the adhesive layer is preferably 2.5-9 μm, preferably 2.5-8.6 μm, more preferably 2.5-8.3 μm, such as 2.5-7.7 μm, 2.5-7.3 μm, 2.5-6.9 μm, and 2.5-6.9 μm. Either of 6.5 μm.

The thickness of the adhesive layer (for example, T _a ) is not particularly limited as long as it does not impair the effect of the present invention, and it is preferable to satisfy the conditions of the above-mentioned S value and L value. For example, the thickness of the adhesive layer may be 1.5-9 μm.

Also, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer, for example, the thickness of an adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer. From such a viewpoint, the minimum value and the maximum value of the thickness of the said adhesive agent layer are prescribed|regulated.

The adhesive layer contains an adhesive. Examples of the aforementioned adhesive include adhesives such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. Resin, preferably acrylic resin.

In the present invention, the so-called "adhesive resin" includes the concept of both adhesive resin and adhesive resin. For example, not only the resin itself has adhesiveness, but also includes other components such as additives used in combination. Resins that exhibit adhesiveness, and resins that exhibit adhesiveness due to the presence of triggers such as heat or water, etc.

The adhesive layer is preferably transparent. The adhesive layer can also be colored according to the purpose. For example, when the film for protective film formation is energy ray curable, it is preferable that the adhesive layer transmits energy ray.

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

>>Adhesive composition>> For the adhesive layer, an adhesive composition having an adhesive can be used. For example, the adhesive layer can be formed at the target site by applying the adhesive composition on the surface to be formed of the adhesive layer and drying it as necessary. A more specific method of forming the adhesive layer will be described in detail later together with methods of forming other layers. In the adhesive composition, the content ratio of components that do not vaporize at normal temperature is usually the same as the content ratio of the aforementioned components of the adhesive layer.

In this specification, "normal temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, for example, a temperature of 15 to 25° C. is mentioned.

The coating of the adhesive composition may be carried out using a known method, for example, an air knife coater, a blade coater, a rod coater, a gravure coater, a roll coater, a roller Various coating methods such as knife coater, curtain coater, die coater, knife coater, screen coater, wire-wound bar coater, lick roll coater, etc.

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

When the adhesive layer is energy ray curable, as an adhesive composition containing an energy ray curable adhesive, that is, an energy ray curable adhesive composition, for example, a non-energy ray curable adhesive resin (I -1a) (hereafter, it may be abbreviated as "adhesive resin (I-1a)"), and an adhesive composition (I-1) of an energy ray-curable compound; containing a non-energy ray-curable adhesive resin Adhesive composition ( I-2); and an adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a) and an energy ray-curable compound.

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

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

Examples of the alkyl (meth)acrylate include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched. As the alkyl (meth)acrylate, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl methacrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, Isononyl (meth)acrylate, Decyl (meth)acrylate, Undecyl (meth)acrylate, Lauryl (meth)acrylate (Lauryl (meth)acrylate), Decyl (meth)acrylate Triester, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmyl (meth)acrylate), ( Heptadecyl methacrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), nonadecyl (meth)acrylate, eicosyl (meth)acrylate, and the like.

In terms of improving the adhesion of the adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms. Moreover, in terms of further enhancing the adhesive force of the adhesive layer, the carbon number of the aforementioned alkyl group is preferably 4-12, more preferably 4-8. Also, the alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms is preferably an alkyl acrylate.

The acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate. As the aforementioned functional group-containing monomer, for example, the aforementioned functional group becomes a starting point of crosslinking by reacting with a crosslinking agent described later, or the aforementioned functional group reacts with an unsaturated group in an unsaturated group-containing compound described later. On the other hand, it is possible to introduce an unsaturated group into a side chain of an acrylic polymer.

As said functional group in a functional group containing monomer, a hydroxyl group, a carboxyl group, an amino group, an epoxy group etc. are mentioned, for example. That is, as a functional group containing monomer, a hydroxyl group containing monomer, a carboxyl group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as hydroxypropyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohols (unsaturated alcohols not having a (meth)acryl skeleton) and the like.

As the aforementioned carboxyl group-containing monomers, for example, ethylenically unsaturated monocarboxylic acids (that is, monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, Ethylenically unsaturated dicarboxylic acids such as itaconic acid, maleic acid, citraconic acid (that is, dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; methyl Carboxyalkyl (meth)acrylate, such as 2-carboxyethyl acrylate, etc.

The functional group-containing monomers are preferably hydroxyl-containing monomers and carboxyl-containing monomers, and more preferably hydroxyl-containing monomers.

The functional group-containing monomer constituting the above-mentioned acrylic polymer may be only one type, or may be two or more types. When there are two or more types, such combinations and ratios can be selected arbitrarily.

In the aforementioned acrylic polymer, the content of structural units derived from functional group-containing monomers is preferably 1-35% by mass, more preferably 2-30% by mass, and 3-30% by mass relative to the total amount of structural units. 27% by mass is particularly preferred.

The said acrylic polymer may further have the structural unit derived from another monomer other than the structural unit derived from an alkyl (meth)acrylate, and the structural unit derived from a functional group containing monomer. The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylate or the like. Examples of the other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.

The said other monomer which comprises the said acrylic polymer may be only 1 type, and may be 2 or more types, and when there are 2 or more types, the combination and ratio of these can be arbitrarily selected.

The aforementioned acrylic polymer can be used as the aforementioned non-energy ray-curable adhesive resin (I-1a). On the other hand, the functional group in the aforementioned acrylic polymer reacts an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group), which can be used as the aforementioned energy ray polymer. Hardening adhesive resin (I-2a).

The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only 1 type, or may be 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

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

[Energy Beam Curing 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 are curable by irradiation with energy ray. Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, neopentylthritol (meth)acrylate, neopentylthritol tetra(meth)acrylate poly(meth)acrylates such as di-neopentylthritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc. Acrylates; Urethane (meth)acrylates; Polyester (meth)acrylates; Polyether (meth)acrylates; Epoxy (meth)acrylates, etc. Among the energy ray-curable compounds, examples of the oligomers include oligomers obtained by polymerizing the monomers exemplified above, and the like. From the viewpoint that the storage elastic modulus of the adhesive layer is not easily lowered because the molecular weight is large, the energy ray-curable compound is based on urethane (meth)acrylate, urethane (meth)acrylate oligomeric Polymers are preferred.

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

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

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

The said crosslinking agent reacts with the said functional group, and crosslinks adhesive resin (I-1a) mutually, for example. Examples of the cross-linking agent include isocyanate-based cross-linking agents (those having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates. cross-linking agent); epoxy-based cross-linking agent such as ethylene glycol glycidyl ether (cross-linking agent with glycidyl group); hexa[1-(2-methyl)-aziridine] Aziridine-based cross-linking agents such as phosphatriazine (cross-linking agents having an aziridine group); metal chelate-based cross-linking agents such as aluminum chelates (cross-linking agents having a metal chelate structure) ); isocyanate-based crosslinking agent (crosslinking agent having isocyanuric acid skeleton) and the like. In terms of increasing the cohesive force of the adhesive to increase the cohesive force of the adhesive layer, and in terms of ease of acquisition, the crosslinking agent is preferably an isocyanate-based crosslinking agent.

The crosslinking agent contained in the adhesive composition (I-1) may be 1 type or 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

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

[Photopolymerization Initiator] The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator fully advances hardening reaction even when irradiated with energy rays of relatively low energy such as ultraviolet rays.

(thioxanthone)等的9-氧硫𠮿

化合物；過氧化物化合物；聯乙醯等的二酮化合物；二苯基乙二酮(benzil)；聯苄(dibenzyl)；二苯基酮；2,4-二乙基9-氧硫𠮿

；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。 又，作為前述光聚合起始劑，例如亦能夠使用1-氯蒽醌等的醌化合物；胺等的光敏化劑等。Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin Benzoin compounds such as methyl benzoate and benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy Acetophenone compounds such as -1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-tri Acyl phosphine oxide compounds such as toluyl diphenyl phosphine oxide; thioether compounds such as benzyl phenyl sulfide (sulfide), tetramethylthiuram monosulfide; 1-hydroxycyclohexylbenzene α-keto alcohol compounds such as ketones; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; 9-oxothiophene

(thioxanthone) and other 9-oxosulfur 𠮿

Compounds; peroxide compounds; diketone compounds such as diacetyl; benzil; dibenzyl; diphenyl ketone; 2,4-diethyl 9-oxythiol

; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone, etc. Moreover, as said photoinitiator, the quinone compound, such as 1-chloroanthraquinone, the photosensitizer, etc. of an amine, etc. can also be used, for example.

The photopolymerization initiator contained in the adhesive composition (I-1) may be 1 type, or may be 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, relative to 100 parts by mass of the content of the aforementioned energy ray-curable compound. Best, especially preferably 0.05-5 parts by mass.

[Other additives] The adhesive composition (I-1) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion imparting agents, reactive Retardant, cross-linking accelerator (catalyst) and other known additives. In addition, the so-called reaction delay agent, for example, suppresses unintended cross-linking reactions of the adhesive composition (I-1) during storage by the action of a catalyst mixed into the adhesive composition (I-1). things. As a reaction delay agent, for example, a compound that forms a chelate complex with a chelate to a catalyst, and more specifically, a compound having two or more carbonyl groups (-C( =O)-).

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

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

[solvent] The adhesive composition (I-1) may also contain a solvent. When the adhesive composition (I-1) contains a solvent, the coating suitability to the surface to be coated improves.

The aforementioned solvent is preferably an organic solvent, and as the aforementioned organic solvent, for example, ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (that is, carboxylate); ethers such as tetrahydrofuran and dioxane; ; Aliphatic hydrocarbons such as cyclohexane and n-hexane; Aromatic hydrocarbons such as toluene and xylene; Alcohols such as 1-propanol and 2-propanol, etc.

As the aforementioned solvent, for example, what is used in the production of the adhesive resin (I-1a) may be used directly in the adhesive composition (I-1) without removing it from the adhesive resin (I-1a). , when producing the adhesive composition (I-1), you may additionally add the same or different solvent to that used for producing the adhesive resin (I-1a).

The solvent contained in the adhesive composition (I-1) may be 1 type or 2 or more types, and when 2 or more types are used, the combination and ratio of these can 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)> The aforementioned adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2a) obtained by introducing unsaturated groups into the side chains of the non-energy ray-curable adhesive resin (I-1a) as described above. ).

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

The aforementioned unsaturated group-containing compound has, in addition to the aforementioned energy ray-polymerizable unsaturated group, a bond capable of bonding with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). The compound of the base of the knot. Examples of the aforementioned energy ray polymerizable unsaturated group include (meth)acryl, vinyl (also called ethenyl), allyl (also called 2-propenyl), and the like. ) acryl group is preferred. Examples of groups capable of bonding to functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups capable of bonding to hydroxyl or amine groups, and groups capable of bonding to carboxyl or epoxy groups. The hydroxyl group and amino group of the junction.

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

The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only 1 type, or may be 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

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

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

Examples of the crosslinking agent in the adhesive composition (I-2) include the same ones as the crosslinking agent in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-2) may be 1 type or 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

In the aforementioned adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2a). Best, especially preferably 0.3-15 parts by mass.

[Photopolymerization Initiator] The adhesive composition (I-2) may further contain a photopolymerization initiator. Even if the adhesive composition (I-2) containing a photoinitiator is irradiated with low-energy energy rays, such as an ultraviolet-ray, hardening reaction fully progresses.

Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same ones as the photopolymerization initiator in the adhesive composition (I-1). The photoinitiator contained in an adhesive composition (I-2) may be only 1 type, and may be 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

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

[Other additives] The adhesive composition (I-2) may contain other additives not belonging to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the other additives in the adhesive composition (I-2) include the same ones as the other additives in the adhesive composition (I-1). The other additive contained in the adhesive composition (I-2) may be only one type, or may be two or more types, and in the case of two or more types, such combinations and ratios can be arbitrarily selected.

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

[solvent] The adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). Examples of the aforementioned solvent in the adhesive composition (I-2) include the same ones as the solvent in the adhesive composition (I-1). The solvent contained in the adhesive composition (I-2) may be 1 type or 2 or more types, and when 2 or more types are used, the combination and ratio of these can 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)> The said adhesive composition (I-3) contains the said adhesive resin (I-2a) and an energy ray curable compound as mentioned above.

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

[Energy Beam Curing Compound] Examples of the aforementioned 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 cured by irradiation with energy ray; and Examples thereof include the same ones as the energy ray-curable compound contained in the adhesive composition (I-1). The said energy ray curable compound contained in an adhesive composition (I-3) may be 1 type, and may be 2 or more types, and when there are 2 or more types, the combination and ratio of these can be arbitrarily selected.

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

[Photopolymerization Initiator] The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photoinitiator fully progressed hardening reaction even when it irradiated the energy ray of low energy, such as an ultraviolet-ray.

Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same ones as the photopolymerization initiator in the adhesive composition (I-1). The photopolymerization initiator contained in the adhesive composition (I-3) may be 1 type, or may be 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

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

[Other additives] The adhesive composition (I-3) may contain other additives not belonging to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the aforementioned other additives include the same ones as the other additives in the adhesive composition (I-1). The other additive contained in the adhesive composition (I-3) may be only 1 type, or may be 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

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

[solvent] The adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). Examples of the aforementioned solvent in the adhesive composition (I-3) include the same ones as the solvent in the adhesive composition (I-1). The solvent contained in the adhesive composition (I-3) may be only one type, or may be two or more types, and in the case of two or more types, such combinations and ratios can be arbitrarily selected. In the adhesive composition (I-3), the content of the solvent is not particularly limited, and may be appropriately adjusted.

> Adhesive compositions other than adhesive compositions (I-1) to (I-3)> So far, although the adhesive composition (I-1), adhesive composition (I-2) and adhesive composition (I-3) have been mainly described, what has been described as these components can be Similarly used for all adhesive compositions other than these three types of adhesive compositions (in this specification, also referred to as "adhesive compositions other than adhesive compositions (I-1) to (I-3)" ).

As the adhesive composition other than the adhesive compositions (I-1) to (I-3), in addition to the energy ray-curable adhesive composition, a non-energy ray-curable adhesive composition is also mentioned. Examples of non-energy ray curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, The adhesive composition (I-4) containing a non-energy ray-curable adhesive resin (I-1a), such as an ester resin, preferably contains an acrylic resin.

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

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

[Adhesive resin (I-1a)] Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same 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 1 type, and may be 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

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

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

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

Examples of the crosslinking agent in the adhesive composition (I-4) include the same ones as the crosslinking agent in the adhesive composition (I-1). The crosslinking agent contained in the adhesive composition (I-4) may be only one type, or may be two or more types, and in the case of two or more types, such combinations and ratios can be arbitrarily selected.

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

[Other additives] The adhesive composition (I-4) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effect of the present invention. Examples of the aforementioned other additives include the same ones as the other additives in the adhesive composition (I-1). The other additive contained in the adhesive composition (I-4) may be only 1 type, or may be 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

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

[solvent] The adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1). Examples of the aforementioned solvent in the adhesive composition (I-4) include the same ones as the solvent in the adhesive composition (I-1). The solvent contained in the adhesive composition (I-4) may be only one type, or may be two or more types, and in the case of two or more types, such combinations and ratios can be arbitrarily selected. In the adhesive composition (I-4), the content of the solvent is not particularly limited, and may be appropriately adjusted.

In the composite sheet for forming a protective film, the adhesive layer is preferably non-energy ray curable. This is because when the adhesive layer is energy ray curable and the thin film for forming a protective film is cured by irradiating energy rays, the adhesive layer cannot be suppressed from being cured at the same time. When the adhesive layer and the film for forming a protective film are cured at the same time, the film for forming a protective film (that is, the protective film) after curing and the adhesive layer may adhere to such an extent that they cannot be peeled off at the interface. At this time, it is difficult to peel off the support sheet provided with the hardened adhesive layer for the semiconductor wafer (semiconductor wafer with protective film) provided with the film for forming the protective film after hardening, that is, the protective film on the back surface, and it is impossible to remove the hardened adhesive layer normally. Pickup of semiconductor wafers with protective film. In the support sheet, by making the adhesive layer non-energy ray curable, such a defect can be reliably avoided and the semiconductor wafer with the protective film can be picked up more easily.

Here, the effect when the adhesive layer is non-energy ray curable has been described, but even if the layer in direct contact between the support sheet and the film for forming a protective film is a layer other than the adhesive layer and the layer is non-energy ray curable, The same effect can also be achieved.

>>Manufacturing method of adhesive composition>> Adhesive compositions other than adhesive compositions (I-1) to (I-3), such as adhesive compositions (I-1) to (I-3), and adhesive composition (I-4), It can be obtained by preparing the above-mentioned adhesive, components other than the above-mentioned adhesive, and the like as needed to constitute the adhesive composition. The addition order at the time of compounding of each component is not specifically limited, You may add 2 or more types of components simultaneously. When using a solvent, it is also possible to mix the solvent with any of the prepared ingredients other than the solvent, and to use the prepared ingredients by diluting the prepared ingredients in advance, or to mix the solvent with the prepared ingredients without pre-diluting any of the prepared ingredients other than the solvent. The ingredients are mixed and used. There is no particular limitation on the method of mixing the ingredients during preparation, and it can be appropriately selected from known methods such as a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing by using a mixer, and a method of mixing by applying ultrasonic waves. That's it. The temperature and time for the addition and mixing of each component are not particularly limited as long as the components are not deteriorated, and can be adjusted appropriately. The temperature is preferably 15~30°C

◎Films for protective film formation The said thin film for protective film formation becomes a protective film directly by hardening or the state which does not make it harden. 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 protective film formation is soft and can be easily attached to an attachment object.

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

In this specification, "non-curable" means the property of not being cured by any means such as heating or irradiation of energy rays. In the present invention, as long as the laminate structure of the hardened product of the support sheet and the protective film forming film (in other words, the support sheet and the protective film) can be maintained even after the film for forming the protective film is cured, the laminate is called "protective film". forming a composite sheet".

Regardless of the type, the film for forming a protective film may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers. When the thin film for protective film formation consists of plural layers, these plural layers may be mutually same or different.

Here, the adhesive layer and the film for protective film formation are demonstrated in more detail, referring FIG. 4 again. As described above, the first surface 11a of the substrate 11 is a concave-convex surface. However, since the R value of the adhesive layer 12 is less than 5.0, the influence of the uneven surface can be suppressed, and the degree of unevenness on the first surface 12 a of the adhesive layer 12 tends to be small. Therefore, the laminarity of the adhesive layer 12 and the film 13 for protective film formation becomes favorable easily. Moreover, when the said S value is 1.5 micrometers or more, the influence of this uneven surface can be suppressed, and the unevenness|corrugation degree on the 1st surface 12a of the adhesive layer 12 becomes small. For example, between the adhesive layer 12 and the film 13 for forming a protective film, even if there are such unbonded regions (non-bonded regions) 92, the number of them exceeds that of the protective film forming composite sheet 1A in the protective film forming composite sheet 1A. The entire area where the thin film 13 is formed is very small, such as three places or less. The said non-bonding area|region 92 can be confirmed easily by observing 1 A of composite sheets for protective film formation from the base material 11 side, for example.

Furthermore, even if the composite sheet 1A for forming a protective film has such a non-bonding region 92, the size (distance between layers) of the non-bonding region 92 in the thickness direction of the composite sheet 1A for forming a protective film is, for example, 0.5 μm or less. In the forming composite sheet 1A, the laminarity between the adhesive layer 12 and the film 13 for forming a protective film is relatively good. Here, "the size of the non-bonding 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 (interlayer distance) of the non-adhesive region 92 is the same as the aforementioned interlayer distance (size) of the non-adhered region 91, preferably 0.5 μm or less, for example, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less. and 0.1 μm or less.

The size (distance between layers) of the non-bonding region 92 can be obtained using the same method as the size (distance between layers) of the above-mentioned non-bonding region 91 except for the point that the combination of the two layers of the object is different.

In 1A of composite sheets for protective film formation, the non-bonding area|region 92 may not exist at all. In this specification, when the non-bonding region 92 does not exist at all, the size (distance between layers) of the non-bonding region 92 may be described as 0 μm.

On the other hand, as described above, the degree of unevenness on the first surface 12 a of the adhesive layer 12 tends to be small. Therefore, the thickness T _p of the film 13 for forming a protective film is not constant, and varies depending on the location of the film 13 for forming a protective film (adhesive layer 12 ), but the range of variation is very small.

Furthermore, as described above, since the unevenness on the first surface 12a of the adhesive layer 12 tends to be small, the surface (second surface) 13b on the side of the adhesive layer 12 of the film 13 for forming a protective film is smooth or uneven. Easy to get smaller. Therefore, the appearance of the film 13 for protective film formation is less likely to be damaged. In addition, the surface (second surface) on the side of the adhesive layer 12 of the protective film formed from the protective film-forming film 13 is also smooth, or the unevenness is reduced, and the appearance of the protective film is easily not damaged. Thus, in 1 A of composite sheets for protective film formation, both the thin film 13 for protective film formation, and a protective film can have excellent design property.

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

The above-mentioned maximum height difference on the second surface 13b of the film 13 for forming a protective film can be, for example, formed a section on a test piece of a composite sheet for forming a protective film or the composite sheet itself for forming a protective film by using the method described above, And it obtained|required by observing this cross section using a scanning electron microscope (SEM).

Here, the protective film-forming composite sheet 1A is taken as an example to describe the adhesive layer and the protective film-forming film. In the case of the composite sheet for film formation, the adhesive layer and the film for protective film formation are the same.

In the protective film-forming composite sheet of the present invention, the thickness of the protective film-forming film (for example, T _p ) 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 protective film formation is more than the said lower limit, the protective film with high protective ability can be formed. Excessive thickness can be suppressed by the thickness of the film for protective film formation being below the said upper limit.

When the thickness of the film for forming a protective film varies depending on the position of the film for forming a protective film, the minimum value of the thickness of the film for forming a protective film may be more than the aforementioned lower limit, and the maximum value of the thickness of the film for forming a protective film may be at least below the aforementioned upper limit.

In addition, the "thickness of the film for forming a protective film" means the thickness of the film for forming a protective film as a whole. The total thickness of the layers.

The thickness of the film for forming a protective film can be measured, for example, by observing the side or cross section of the film for forming a protective film 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 in the cross section of the test piece of the support sheet and the composite sheet for forming a protective film described above.

For example, using the method described above, a test piece is cut from plural places (for example, 5 places) of the composite sheet for forming a protective film, and the minimum and maximum values of the film thickness for forming a protective film are obtained from the test piece. Furthermore, when the average value of these minimum values and the average value of the maximum value are calculated|required, the average value of the said minimum value may be more than the lower limit value of the film thickness for the said protective film formation, and the average value of the said maximum value may be the above-mentioned protective film It is not more than the upper limit value of the film thickness for formation.

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

The coating of the composition for forming a shield may be performed by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roller Various coating methods such as knife coater, curtain coater, die coater, knife coater, screen coater, wire-wound bar coater, lick roll coater, etc.

The drying conditions of the composition for forming a protective film are not particularly limited, but when the composition for forming a protective film contains a solvent described later, it is preferable to dry it by heating. Furthermore, it is preferable to dry the protective film-forming composition containing a solvent, for example, at 70 to 130° C. for 10 seconds to 5 minutes. However, when the composition for forming a protective film is thermosetting, it is preferable to dry the composition for forming a protective film so that the formed thin film for forming a protective film is not cured by thermosetting.

Hereinafter, each type will be demonstrated in detail about the thin film for protective film formation, and the composition for protective film formation.

○Films for thermosetting protective film formation As a preferable film for thermosetting protective film formation, the thing containing a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) can be regarded as a component formed by polymerizing a polymerizable compound. The thermosetting component (B) is a component obtained by performing a curing (polymerization) reaction using heat as a reaction trigger. In addition, the polymerization reaction in the present invention also includes polycondensation reaction.

After sticking the film for forming a thermosetting protective film on the back surface of the semiconductor wafer and then thermosetting it, the curing conditions are not particularly limited as long as the cured product has a degree of curing sufficient to exert its function. What is necessary is just to select suitably for the kind of thin film for thermosetting protective film formation. For example, the heating temperature at the time of thermal curing 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. Furthermore, the heating time during the aforementioned hardening is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.

>Thermosetting protective film forming composition (III-1)> As a preferable composition for forming a thermosetting protective film, for example, a composition (III-1) for forming a thermosetting protective film containing a polymer component (A) and a thermosetting component (B) (in this Instructions, there may be only abbreviated as "composition (III-1)", etc.).

[Polymer component (A)] The polymer component (A) is a component for imparting film formability, flexibility, and the like to the film for forming a thermosetting protective film. The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind or two or more kinds. choose.

Examples of the polymer component (A) include acrylic resins, polyesters, urethane resins, urethane acrylate resins, silicone resins, rubber resins, phenoxy resins, thermosetting Non-volatile polyimide, etc., preferably acrylic resin.

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

In the present specification, the term "weight average molecular weight" means a polystyrene-equivalent value measured using gel permeation chromatography (GPC) unless otherwise specified.

The glass transition temperature (Tg) of acrylic resin is preferably -60~70°C, preferably -30~50°C. When Tg of an acrylic resin is more than the said lower limit, the peelability of a support sheet can be improved suitably, for example while suppressing the adhesive force of the hardened|cured material (that is, a protective film) of the film for protective film formation, and a support sheet. Moreover, when Tg of an acrylic resin is below the said upper limit, the adhesive force of the film for thermosetting protective film formation, a protective film, and an adherend improves.

Moreover, it is not limited to acrylic resins, and the Tg of the resins in this specification can be set at -70°C to Change the temperature of the object to be measured between 150°C and obtain it by confirming the inflection point.

Examples of acrylic resins include one or more (meth)acrylate polymers; selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxy Copolymers of two or more monomers such as methacrylamide, etc.

Examples of the (meth)acrylate constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second-butyl (meth)acrylate, third-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate base) hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-(meth)acrylate Nonyl, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, (meth)acrylic dodecanoic acid (lauryl (meth)acrylate), (meth)acrylate ) tridecyl acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmyl (meth)acrylate ), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc., the alkyl group constituting the alkyl ester is one of the chain structures with 1 to 18 carbon atoms. Alkyl (meth)acrylates; cycloalkyl (meth)acrylates such as isocamphoryl (meth)acrylate and dicyclopentanyl (meth)acrylate; (meth)acrylic acid such as benzyl (meth)acrylate Aralkyl acrylate; cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; (meth)acrylcycloalkenyloxy such as dicyclopentenyloxyethyl (meth)acrylate Alkyl esters; imide (meth)acrylates; glycidyl (meth)acrylates 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, and 4-hydroxybutyl (meth)acrylate; (meth)acrylates containing substituted amino groups such as N-methylaminoethyl (meth)acrylate, etc. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.

The acrylic resin may be, for example, one selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide in addition to the aforementioned (meth)acrylates. A copolymer of one or more monomers.

The monomer which comprises an acrylic resin may be 1 type, and may be 2 or more types, and when there are 2 or more types, the combination and ratio of these can be arbitrarily selected.

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

In the present invention, as the polymer component (A), thermoplastic resins other than acrylic resins (hereinafter abbreviated as "thermoplastic resins") may be used alone without acrylic resins, or together with acrylic resins. Resin is used together. By using the above-mentioned thermoplastic resin, the release property of the protective film from the support sheet is improved, or the film for forming a thermosetting protective film can easily follow the uneven surface of the adherend, and there is further suppression between the adherend and the thermosetting protective film. A case where voids, etc., are generated between thin films for formation.

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

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

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

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

Composition (III-1), regardless of the content ratio of the polymer component (A) (that is, the content of the polymer component (A) of the film for forming a thermosetting protective film) to the total content of all components except the solvent The type of polymer component (A) is preferably 5-85% by mass, more preferably 5-75% by mass, for example, 5-65% by mass, 5-50% by mass, and 10-35% by mass etc. either.

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III-1) contains such a component corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is regarded as containing the polymer component (A ) and thermosetting component (B).

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

Examples of the thermosetting component (B) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins. 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 type, or may be two or more types. When there are two or more types, the combination and ratio of these can be selected arbitrarily.

‧Epoxy resin (B1) Examples of the epoxy resin (B1) include known ones, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ester and its hydride, o-cresol novolak ring Oxygen resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. Oxygen compounds.

An epoxy resin having an unsaturated hydrocarbon group can also be used as the epoxy resin (B1). Compared with epoxy resins without unsaturated hydrocarbon groups, epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the semiconductor wafer with a protective film obtained using the composite sheet for protective film formation improves.

As an epoxy resin which has an unsaturated hydrocarbon group, the compound which converted a part of the epoxy group of a polyfunctional epoxy resin into the group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound can be obtained by, for example, adding (meth)acrylic acid or a derivative thereof to an epoxy group. Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly bonded to the aromatic ring etc. which comprise an epoxy resin are mentioned, for example. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include vinyl (also called vinyl), 2-propenyl (also called allyl), (meth)acryl, (Meth)acrylamide group, etc., preferably acrylyl group.

The number average molecular weight of the epoxy resin (B1) is not particularly limited, but it is preferably 300 to 30,000 from the viewpoint of the curability of the film for forming a thermosetting protective film, and the strength and heat resistance of the cured protective film. 300~10000 is better, especially 300~3000.

In the present specification, the number average molecular weight is a polystyrene-equivalent value measured using gel permeation chromatography (GPC) unless otherwise specified.

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

An epoxy resin (B1) may be used individually by 1 type, or may use 2 or more types together, and when using 2 or more types together, the combination and ratio of these can be arbitrarily selected.

‧Thermal curing agent (B2) The thermosetting agent (B2) can function as a curing agent for the epoxy resin (B1). As a thermosetting agent (B2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the above-mentioned functional group, for example, phenolic hydroxyl group, alcoholic hydroxyl group, amino group, carboxyl group, and acid group are anhydroused, etc., preferably, phenolic hydroxyl group, amino group, or acidic group are anhydroused. A phenolic hydroxyl group or an amino group is preferred.

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

The thermosetting agent (B2) may have an unsaturated hydrocarbon group. Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which a part of the hydroxyl groups of a phenol resin is substituted by a group having an unsaturated hydrocarbon group, and aromatic compounds in which a group having an unsaturated hydrocarbon group is directly bonded to a phenol resin. Compounds formed from rings, etc. The aforementioned unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group of the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

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

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

A thermosetting agent (B2) may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, the combination and ratio of these can be arbitrarily selected.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 to 500 parts by mass based on 100 parts by mass of the epoxy resin (B1). 1-200 mass parts is preferable, For example, any one of 1-100 mass parts, 1-50 mass parts, 1-25 mass parts, and 1-10 mass parts etc. is sufficient. When the said content of a thermosetting agent (B2) is more than the said lower limit, hardening of the thin film for thermosetting protective film formation will progress more easily. Moreover, when the said content of a thermosetting agent (B2) is below the said upper limit, the moisture absorption rate of the film for thermosetting protective film formation can be reduced, and the reliability of the package obtained using the composite sheet for protective film formation can be reduced. Sex is further enhanced.

In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (such as epoxy resin (B1) and The total content of the thermosetting agent (B2) is preferably 20-500 parts by mass, more preferably 30-300 parts by mass, more preferably 40-150 parts by mass, for example, 45-100 parts by mass, and 50-300 parts by mass. Either 80 parts by mass or the like. When the content of the thermosetting component (B) is in such a range, for example, the adhesive force between the cured product of the film for protective film formation and the support sheet can be suppressed, and the peelability of the support sheet can be improved.

[Hardening Accelerator (C)] The composition (III-1) for protective film formation and the film for thermosetting protective film formation may contain hardening accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the composition (III-1) for forming a protective film. As a preferred hardening accelerator (C), for example, the third group of triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl) phenol, etc. Class amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl -Imidazoles such as 5-hydroxymethylimidazole (imidazoles in which more than one hydrogen atom is replaced by a group other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (1 more than one hydrogen atom substituted by an organic group); tetraphenylphosphonium tetraphenyl borate, tetraphenyl boron salt of triphenylphosphine tetraphenyl borate, etc.

The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type, or two or more types. to choose.

When the hardening accelerator (C) is used, in the composition (III-1) and the film for forming a thermosetting protective film, the content of the hardening accelerator (C) is 100 parts by mass relative to the content of the thermosetting component (B), It is preferably 0.01-10 parts by mass, more preferably 0.1-7 parts by mass. When the said content of a hardening accelerator (C) is more than the said lower limit, the effect obtained by using a hardening accelerator (C) can become more remarkable. In addition, when the content of the hardening accelerator (C) is not more than the aforementioned upper limit, it is possible to suppress, for example, the high-polarity hardening accelerator (C) from interfering with the substrate in the film for forming a thermosetting protective film under high temperature and high humidity conditions. The effect of segregation by movement of the adhesive interface side of the sticky material becomes higher, and the reliability of the semiconductor wafer with a protective film obtained by using the composite sheet for forming a protective film is further improved.

[Filler (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 thermosetting protective film formation, it becomes easy to adjust the said water absorption rate and adhesive force change rate so that they may exist in the target range. Moreover, by containing the filler (D) in the film for forming a thermosetting protective film and the protective film, it is easy to adjust the number of thermal expansion, and by making the number of thermal expansion relative to the film for forming a thermosetting protective film or the object to be formed of the protective film For optimization, the reliability of the semiconductor wafer with protective film obtained by using the composite sheet for protective film formation is further improved. Moreover, when the film for thermosetting protective film formation contains a filler (D), the moisture absorption rate of a protective film can also be reduced, and heat dissipation can be improved.

The filler (D) can be any of organic fillers and inorganic fillers, preferably inorganic fillers. Preferable inorganic fillers include, for example, powders of silicon oxide, alumina, talc, calcium carbonate, titanium dioxide, red iron powder, silicon carbide, boron nitride, etc.; these inorganic fillers are spheroidized beads; surface modified products of such inorganic fillers; single crystal fibers of such inorganic fillers; and glass fibers, etc. Among them, the inorganic filler is preferably silicon oxide or aluminum oxide, 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 type, or may be two or more types. When there are two or more types, the combination and ratio of these can be arbitrary. to choose.

When the filler (D) is used, in the composition (III-1), relative to the total content of all components other than the solvent, the ratio of the content of the filler (D) (that is, the film for forming a thermosetting protective film The content of the filler (D)) is preferably 5-80% by mass, more preferably 10-70% by mass, for example, 20-65% by mass, 30-65% by mass, and 40-65% by mass, etc. either. When the content of the filler (D) is within such a range, it is easier to adjust the above-mentioned coefficient of thermal expansion, and the film for protective film formation and the strength of the protective film are further improved.

[Coupling agent (E)] The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using what has the functional group which can react with an inorganic compound or an organic compound as a coupling agent (E), the adhesiveness and adhesiveness of the film for thermosetting protective film formation to an adherend can be improved. Moreover, by using a coupling agent (E), the hardened|cured material (protective film) of the thin film for thermosetting protective film formation does not impair heat resistance, and water resistance improves.

The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group possessed by the polymer component (A) or the thermosetting component (B), and is preferably a silane coupling agent. As a preferred aforementioned silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Propyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyl Methyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-acylurea (ureide)propyltrimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide (sulfane), methyltrimethoxysilane , Methyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriacetoxysilane, 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 type, or may be two or more types. When there are two or more types, the combination and ratio of these can be arbitrary. to choose.

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

[Crosslinking agent (F)] As the polymer component (A), when using a functional group such as the above-mentioned acrylic resin, such as a vinyl group, (meth)acryl group, amine group, hydroxyl group, carboxyl group, isocyanate group, etc. , The composition (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F). The cross-linking agent (F) is a component for cross-linking the aforementioned functional group in the polymer component (A) with other compounds. Through such cross-linking, it is possible to adjust the thickness of the film for forming a thermosetting protective film. Initial adhesion and cohesion.

Examples of the crosslinking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents, etc. agent (crosslinking agent with aziridine group), etc.

Examples of the organic polyvalent isocyanate compound include 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.") case); trimers, isocyanate bodies, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc., with polyol compounds, etc. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil, etc. Reactant of low molecular active hydrogen compounds. As an example of the said adduct, the xylylene diisocyanate adduct of trimethylolpropane mentioned later etc. are mentioned. Also, the "isocyanate-terminated urethane prepolymer" is as described above.

As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-mylene diisocyanate; 2,6-mylene diisocyanate; 1,3-xylylene diisocyanate; 1,4- Xylene diisocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-Methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Phorne diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylolpropane and other polyols, all or part of the hydroxy added toluene di Any one or two or more compounds of isocyanate, hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

Examples of the aforementioned organic polyimine compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-acridine Cyclopropanyl propionate, tetramethylolmethane-tri-β-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridine carboxamide) triethylene base melamine etc.

When using an organic polyvalent isocyanate compound 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, by reacting the crosslinking agent (F) with the polymer component (A), it is possible to easily introduce a crosslinked structure into the thermosetting protection A thin film for film formation.

The crosslinking agent (F) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. When there are two or more types, the combination and ratio of these can Choose arbitrarily.

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

[energy ray curable resin (G)] The composition (III-1) may contain an energy ray curable resin (G). The thin film for thermosetting protective film formation can change a characteristic by irradiating an energy ray by containing an energy ray curable resin (G).

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

Examples of the acrylate-based compounds include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, neopentylitol tri(meth)acrylate, neopentylthritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Dineopentylthritol monohydroxypenta(meth)acrylate, Dineopentaerythritol hexa(meth)acrylate, 1,4-Butanediol bis(meth)acrylate ) acrylate, 1,6-hexanediol di(meth)acrylate and other (meth)acrylates containing chain aliphatic skeleton; dicyclopentanyl di(meth)acrylate and other containing cycloaliphatic skeleton (meth)acrylates; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylates; oligoester (meth)acrylates; urethane (meth)acrylates base) acrylate oligomers; epoxy-modified (meth)acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itaconic acid oligomers, etc. .

The weight average molecular weight of the energy ray-curable compound is preferably 100-30000, more preferably 300-10000.

The energy ray-curable compound used for polymerization may be 1 type, or 2 or more types, and when 2 or more types are used, the combination and ratio of these can be arbitrarily selected.

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

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

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

(thioxanthone)等的9-氧硫𠮿

化合物；過氧化物化合物；聯乙醯等的二酮化合物；二苯基乙二酮(benzil)；聯苄(dibenzyl)；二苯基酮；2,4-二乙基9-氧硫𠮿

；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。又，作為前述光聚合起始劑，例如亦能夠使用1-氯蒽醌等的醌化合物；胺等的光敏化劑等。Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Benzoin compounds such as ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, etc.; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane- Acetophenone compounds such as 1-ketone and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl)benzene Acyl phosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyl diphenyl phosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide Compounds; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; 9-oxosulfur

(thioxanthone) and other 9-oxosulfur 𠮿

Compounds; peroxide compounds; diketone compounds such as diacetyl; benzil; dibenzyl; diphenyl ketone; 2,4-diethyl 9-oxythiol

; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone, etc. Moreover, as said photoinitiator, the quinone compound, such as 1-chloroanthraquinone, the photosensitizer, etc. of an amine, etc. can also be used, for example.

The photoinitiator (H) contained in composition (III-1) may be 1 type, and may be 2 or more types, and when it is 2 or more types, the combination and ratio of these can be arbitrarily selected.

When using a photopolymerization initiator (H), the content of the photopolymerization initiator (H) in the composition (III-1) is 0.1 to 20 parts by mass relative to 100 parts by mass of the energy ray-curable resin (G). Parts by mass are preferred, preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass.

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

Examples of the aforementioned organic pigments and organic dyes include amine-based dyes, cyanine-based dyes, merocyanidin-based dyes, croconium-based dyes, squalium-based dyes, Azulenium-based pigments, polymethine-based pigments, naphthoquinone-based pigments, pyrylium-based pigments, phthalocyanine-based pigments, naphthalocyanine-based pigments, naphthalenamide ( naphtholactam) pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, quinacridone pigments, isoindoline Dorinone dyes, quinophthalone dyes, pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex dyes), dithiol metal complex dyes, Indoxyl-based pigments, triallylmethane-based pigments, anthraquinone-based pigments, di㗁-based pigments, naphthol-based pigments, imine-based pigments, benzimidazolone-based pigments, and pyranthron-based pigments Pigments and threne-based colors, etc.

Examples of the aforementioned inorganic pigments include carbon black, cobalt-based pigments, ferric pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO ( Indium tin oxide) based pigments, ATO (antimony tin oxide) based pigments, etc.

The coloring agent (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be 1 type, or 2 or more types, and when there are 2 or more types, the combination and ratio of these can be arbitrary. to choose.

When using a coloring agent (I), what is necessary is just to adjust content of the coloring agent (I) of the film for thermosetting protective film formation suitably according to the objective. For example, by adjusting the content of the coloring agent (I) in the thermosetting protective film-forming film and adjusting the light transmittance of the protective film, the visibility of printed characters can be adjusted when laser printing is performed on the protective film. Moreover, by adjusting the content of the coloring agent (I) of the thin film for thermosetting protective film formation, the design property of a protective film can be improved, and the grinding mark on the back surface of a semiconductor wafer can also be made difficult to see. In consideration of this point, the content ratio of the coloring agent (I) (that is, the coloring of the thermosetting protective film forming film) relative to the total content of all components other than the solvent of the protective film forming composition (III-1) The content of agent (I)) is preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and particularly preferably 0.1 to 5% by mass. When the said content of a coloring agent (I) is more than the said lower limit, the effect obtained by using a coloring agent (I) can become more remarkable. Moreover, when the said content of a coloring agent (I) is below the said upper limit, it can suppress that the light transmittance of the film for thermosetting protective film formation falls too much.

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

The general-purpose additive (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or may be two or more types. When there are two or more types, the combination and ratio of these can be Choose arbitrarily. The content of the general-purpose additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.

[solvent] Composition (III-1) preferably further contains a solvent. The composition (III-1) for protective film formation containing a solvent can make handleability favorable. The aforementioned solvents are not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1-butanol Alcohols such as alcohol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; Amides such as dimethylformamide and N-methylpyrrolidone (with amide Compounds with amine bonds), etc. The solvent contained in the composition (III-1) may be only one kind, or two or more kinds. When there are two or more kinds of solvents, the combinations and ratios thereof can be arbitrarily selected.

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

>>Method for producing thermosetting protective film-forming composition>> Compositions for forming a thermosetting protective film such as composition (III-1) can be obtained by preparing each component for constituting the composition. The order of adding each component is not particularly limited, and two or more components may be added at the same time. When using a solvent, the solvent may be mixed with any of the prepared ingredients other than the solvent and used by diluting the prepared ingredients in advance, or may be used without pre-diluting any of the prepared ingredients other than the solvent, and the solvent may be mixed with the prepared ingredients Mixed and used. There is no particular limitation on the method of mixing the ingredients during preparation, and it can be appropriately selected from known methods such as a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing by using a mixer, and a method of mixing by applying ultrasonic waves. Can. The temperature and time of adding and mixing each component are not particularly limited as long as the ingredients are not degraded, and can be adjusted appropriately. The temperature is preferably 15~30°C.

○Films for forming energy ray curable protective films Examples of the energy ray-curable protective film forming film include those containing the energy ray-curable component (a), preferably those containing the energy ray-curable component (a) and a filler. In the film for forming an energy ray curable protective film, the energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and is preferably uncured and has adhesiveness. Here, the so-called "energy ray" and "energy ray curability" are as described above.

There are no particular limitations on the curing conditions when the thin film for forming an energy ray curable protective film is attached to the back of the semiconductor wafer and then cured, as long as the degree of hardening is such that the cured product can fully perform its function. What is necessary is just to select suitably according to the kind of thin film for protective film formation. For example, when curing a film for forming an energy ray curable protective film, the illuminance of the energy ray is preferably 120 to 280 mW/cm ² . In addition, the light quantity of the energy ray at the time of curing is preferably 100~1000mJ/cm ² .

>Energy ray curable protective film forming composition (IV-1)> As a preferable composition for forming an energy ray curable protective film, for example, the composition for forming an energy ray curable protective film (IV-1) containing the aforementioned energy ray curable component (a) can be mentioned (in this specification, there is Only when it is abbreviated as "composition (IV-1)", etc.).

[energy ray hardening ingredient (a)] The energy ray curable component (a) is a component that is cured by irradiation of energy ray, and is used to form a hard film after curing while imparting film-forming properties, flexibility, etc. to the film for forming an energy ray curable protective film. Components of the protective film. Examples of the energy ray-curable component (a) include polymers (a1) having an energy ray-curable group with a weight average molecular weight of 80,000 to 2,000,000, and compounds having an energy ray-curable group with a molecular weight of 100 to 80,000 (a2). At least a part of the aforementioned polymer (a1) may be cross-linked by a cross-linking agent, or may not be cross-linked.

(Polymer (a1) having a weight average molecular weight of 80,000 to 2,000,000 having an energy ray curable group) 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 an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, and an acrylic polymer (a11) having a An acrylic resin (a1-1) obtained by reacting an energy ray-curable compound (a12) having an energy ray-curable group having an energy ray-curable group such as an energy ray-curable double bond and a group reactive with the aforementioned functional group.

Examples of the functional group capable of reacting with groups of other compounds include hydroxyl group, carboxyl group, amino group, substituted amino group (one or two hydrogen atoms of the amino group are replaced by groups other than hydrogen atoms) group), epoxy group, etc. However, from the viewpoint of preventing corrosion of circuits such as semiconductor wafers and semiconductor wafers, the aforementioned functional groups are preferably groups other than carboxyl groups. Among them, the aforementioned functional group is preferably a hydroxyl group.

‧Acrylic polymer with functional groups (a11) Examples of the acrylic polymer (a11) having the aforementioned functional groups include copolymers of acrylic monomers having the aforementioned functional groups and acrylic monomers that do not have the aforementioned functional groups. In addition to other monomers, it is further copolymerized with monomers other than acrylic monomers (non-acrylic monomers). Moreover, the above-mentioned acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method can be used for the polymerization method.

As an acrylic monomer which has the said functional group, a hydroxyl group containing monomer, a carboxyl group containing monomer, an amino group containing monomer, a substituted amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as propyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; vinyl alcohol, olefin Non-(meth)acrylic unsaturated alcohols such as propanols (unsaturated alcohols not having a (meth)acryl skeleton) and the like.

As the aforementioned carboxyl group-containing monomers, for example, ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as acid, maleic acid, and citraconic acid; anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxymethacrylic acid Carboxyalkyl (meth)acrylate such as ethyl ester, etc.

The acrylic monomers containing the aforementioned functional groups are preferably hydroxyl-containing monomers.

The functional group-containing acrylic monomer constituting the acrylic polymer (a11) may be only one type, or may be two or more types. When there are two or more types, such combinations and ratios can be selected arbitrarily.

Examples of acrylic monomers that do not have the aforementioned functional groups include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, Butyl (meth)acrylate, isobutyl (meth)acrylate, second-butyl (meth)acrylate, third-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, (meth)acrylic dodecanoic acid (also known as lauryl (meth)acrylate), (meth)acrylate base) tridecyl acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (also known as (Meth)acrylic palmityl ester), (meth)acrylic acid heptadecyl, (meth)acrylic acid octadecyl (also known as (meth)acrylic acid stearate) and other alkyl esters are carbon numbers It is an alkyl (meth)acrylate with a chain structure of 1~18.

Moreover, as an acrylic monomer which does not have the said functional group, the methoxymethyl (meth)acrylate, the methoxyethyl (meth)acrylate, the ethoxymethyl (meth)acrylate, etc. are also mentioned, for example. Alkoxyalkyl-containing (meth)acrylates such as esters, ethoxyethyl (meth)acrylates, etc.; aromatic (meth)acrylates such as aryl (meth)acrylates such as phenyl (meth)acrylates, etc. (Meth)acrylates; non-crosslinkable (meth)acrylamide and its derivatives; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethacrylate Non-crosslinkable tertiary amine groups (meth)acrylates such as methylaminopropyl ester, etc.

The acrylic monomer which does not have the said functional group which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types.

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

In the acrylic polymer (a11), the ratio (content) of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting it is preferably 0.1 to 50% by mass. , preferably 1 to 40% by mass, particularly preferably 3 to 30% by mass. With the aforementioned ratio in such a range, in the aforementioned acrylic resin (a1-1) obtained by copolymerizing the aforementioned acrylic polymer (a11) and the aforementioned energy ray-curable compound (a12), the energy ray-curable group The content of can easily adjust the hardening degree of the protective film to a preferable range.

The said acrylic polymer (a11) which comprises the said acrylic resin (a1-1) may be only 1 type, and may be 2 or more types, and when there are 2 or more types, the combination and ratio of these can be arbitrarily selected.

In the composition (IV-1), the content ratio of the acrylic resin (a1-1) relative to the total content of components other than the solvent (that is, the acrylic resin (a1-1) of the film for forming an energy ray curable protective film The content of 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 aforementioned energy ray-curable compound (a12) has one or more kinds selected from the group consisting of isocyanate group, epoxy group, and carboxyl group as the functional group capable of reacting with the aforementioned acrylic polymer (a11). Those having an isocyanate group as the aforementioned group are preferred. For example, when the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

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

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

The aforementioned energy ray-curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be one type or two or more types, and when there are two or more types, the combinations and ratios thereof can be selected arbitrarily.

The ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) in the acrylic resin (a1-1) It is preferably 20-120 mol%, more preferably 35-100 mol%, and particularly preferably 50-100 mol%. When the ratio of the said content is such a range, the adhesive force of the protective film after hardening becomes large. Also, when the aforementioned energy ray-curable compound (a12) is a monofunctional (having one of the aforementioned groups in one molecule) compound, the upper limit of the ratio of the aforementioned content is 100 mol%, and the aforementioned energy ray-curable compound (a12 ) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the ratio of the aforementioned content may exceed 100 mol%.

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

When at least a part of the aforementioned polymer (a1) is cross-linked by a cross-linking agent, the aforementioned polymer (a1) does not belong to the above-mentioned monomers described in the aforementioned constituents of the acrylic polymer (a11). Either one, and it may be a monomer having a group reactive with a crosslinking agent polymerized and crosslinked at the group reactive with the crosslinking agent, or may be combined with the aforementioned energy ray-curable compound (a12 ) is a product formed by cross-linking with the group reacted with the aforementioned functional group.

The aforementioned polymer (a1) contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be one type or two or more types. When there are two or more types, the combination and ratio of these polymers can Choose arbitrarily.

(Compound (a2) having a molecular weight of 100 to 80,000 having an energy ray hardening group) In the compound (a2) having an energy ray curable group with a molecular weight of 100 to 80000, examples of the energy ray curable group include a group containing an energy ray curable double bond, and preferred examples include (a base) acryl, vinyl, etc.

The aforementioned compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples of low-molecular-weight compounds having energy ray-curable groups include epoxy resins having energy ray-curable groups, and epoxy resins having energy ray-curable groups. Phenolic resin etc.

Among the aforementioned compounds (a2), examples of low-molecular-weight compounds having energy-ray-curable groups include polyfunctional monomers or oligomers, and acrylate-based compounds having (meth)acryl groups are used as examples. good. Examples of the acrylate-based compounds include 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxypropyl bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A bis(methyl) ) acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloxy Ethoxy)phenyl] fennel, 2,2-bis[4-[(meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, 1 , 10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate base) acrylate, tripropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethoxy)phenyl]propane, Neopentyl glycol di(meth)acrylate; 2-functional (meth)acrylate of ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, etc. base) acrylate; ginseng (2-(meth)acryloxyethyl) isocyanate, ε-caprolactone modified ginseng-(2-(meth)acryloxyethyl) isocyanate, ethoxylated Glycerin Tri(meth)acrylate, Neopentylthritol Tri(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Ditrimethylolpropane Tetra(meth)acrylate, Epoxy Neopentylthritol tetra(meth)acrylate, neopentylthritol tetra(meth)acrylate, diperythritol poly(meth)acrylate, diperythritol hexa(meth)acrylate, etc. Multifunctional (meth)acrylates; Polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers, etc.

Among the aforementioned compounds (a2), as the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group, for example, those described in paragraph 0043 of "JP-A-2013-194102" can be used. thing. Such a resin also corresponds to a resin constituting a thermosetting component described later, but is treated as the aforementioned compound (a2) in the present invention.

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

The above-mentioned compound (a2) containing the composition (IV-1) and the thin film for forming an energy ray curable protective film may be only one kind, or may be two or more kinds. choose.

[Polymer (b) not having an energy ray curable group] When the composition (IV-1) and the film for forming an energy ray curable protective film contain the aforementioned compound (a2) as the aforementioned energy ray curable component (a), the polymer (b) having no energy ray curable group may be further contained. ) is preferred. At least a part of the aforementioned polymer (b) may be cross-linked by a cross-linking agent, or may not be cross-linked.

Examples of the polymer (b) not having an energy-ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylate urethane resins. Among them, the above-mentioned polymer (b) is preferably an acrylic polymer (hereinafter abbreviated as "acrylic polymer (b-1)").

The acrylic polymer (b-1) can be a conventional one, for example, it can be a homopolymer of one acrylic monomer; it can also be a copolymer of two or more acrylic monomers; it can also be one Or a copolymer of two or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).

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

Examples of the aforementioned alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate, base) n-butyl acrylate, isobutyl (meth)acrylate, second-butyl (meth)acrylate, third-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, ( Isononyl methacrylate, Decyl (meth)acrylate, Undecyl (meth)acrylate, Lauryl (meth)acrylate (Lauryl (meth)acrylate), Tridecyl (meth)acrylate ester, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate), (meth)acrylate Base) heptadecyl acrylate, octadecyl (meth)acrylate ((meth)acrylic acid stearate), etc. The alkyl group constituting the alkyl ester is (meth)acrylic acid with a chain structure of 1 to 18 carbon atoms Alkyl esters.

Examples of (meth)acrylates having a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; Aralkyl (meth)acrylates such as benzyl (meth)acrylate; Cycloenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; Cycloalkenyloxyalkyl (meth)acrylate, such as dicyclopentenyloxyethyl (meth)acrylate, etc.

As said glycidyl group containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example. (Meth)acrylate containing as said hydroxyl group, for example, (meth)acrylate 2-hydroxyethyl (meth)acrylate, (meth)acrylate 2-hydroxypropyl, (meth)acrylate 3 -Hydroxypropyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. As said substituted amino group containing (meth)acrylate, N-methylamino ethyl (meth)acrylate etc. are mentioned, for example.

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

Examples of the polymer (b) having at least a part of the polymer (b) cross-linked by the cross-linking agent that does not have the aforementioned energy ray-curable groups include those obtained by reacting the reactive functional groups in the aforementioned polymer (b) with the cross-linking agent. . The said reactive functional group should just be suitably selected according to the kind of crosslinking agent etc., and it does not specifically limit. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional groups include hydroxyl group, carboxyl group, amino group, etc. Among them, hydroxyl group having higher reactivity with isocyanate group is preferable. Also, when the crosslinking agent is an epoxy compound, examples of the reactive functional group include carboxyl group, amine group, amido group and the like, and carboxyl group having higher reactivity with epoxy group is preferable. 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 a carboxyl group.

As a polymer (b) which has the said reactive functional group and does not have an energy-ray curable group, the thing obtained by polymerizing the monomer which has the said reactive functional group at least is mentioned, for example. In the case of the acrylic polymer (b-1), use a substance having the aforementioned reactive functional group as the aforementioned acrylic monomer and non-acrylic acid monomers listed as monomers constituting the acrylic polymer (b-1). Either or both of the monomers can be used. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth)acrylate, and the above-mentioned acrylic acid. A monomer or a non-acrylic monomer obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted by the aforementioned reactive functional groups.

In the aforementioned polymer (b) having a reactive functional group, relative to the total amount of structural units constituting the polymer (b), the ratio (content ), preferably 1-20% by mass, more preferably 2-10% by mass. When the aforementioned ratio is in such a range, the degree of crosslinking of the aforementioned polymer (b) becomes a preferable range.

From the standpoint of better film-forming properties of the composition (IV-1), the weight-average molecular weight (Mw) of the polymer (b) not having an energy ray-curable group is preferably 10,000 to 2,000,000. 100000~1500000 is better. Here, the "weight average molecular weight" is as described above.

The polymer (b) not having an energy ray curable group contained in the composition (IV-1) and the film for forming an energy ray curable protective film may be one type or two or more types. These combinations and ratios can be selected arbitrarily.

As a composition (IV-1), what contains either one or both of said polymer (a1) and said compound (a2) is mentioned. Furthermore, when the composition (IV-1) contains the aforementioned compound (a2), it is preferable to further include the polymer (b) not having an energy ray curable group, and in this case, it is also preferable to further include the aforementioned (a1). In addition, the composition (IV-1) may contain the above-mentioned polymer (a1) and the polymer (b) not having an energy ray curable group at the same time without containing the aforementioned compound (a2).

When the composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2) and the polymer (b) having no energy ray curable group, in the composition (IV-1), the aforementioned compound (a2) The content is preferably 10-400 parts by mass, more preferably 30-350 parts by mass, based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) not having an energy-ray-curable group.

In composition (IV-1), with respect to the total content of components other than the solvent, the total content ratio of the aforementioned energy ray curable component (a) and polymer (b) not having an energy ray curable group (that is, The total content of the energy ray curable component (a) and the polymer (b) not having an energy ray curable group) of the film for forming an energy ray curable protective film is preferably 5 to 90% by mass, and 10 to 80% by mass. The mass % is more preferable, and 20-70 mass % is especially preferable. When the ratio of the content of the energy ray curable component is in such a range, the energy ray curability of the thin film for forming an energy ray curable protective film becomes more favorable.

Composition (IV-1) may contain, in addition to the aforementioned energy ray curable components, a thermosetting component selected from a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general-purpose One or two or more of the group consisting of additives.

For example, by using the composition (IV-1) containing the aforementioned energy ray curable component and thermosetting component, the formed thin film for forming an energy ray curable protective film has improved adhesive force to the adherend by heating , and the strength of the protective film formed from the thin film for forming an energy ray curable protective film is also improved. Also, by using the composition (IV-1) containing the aforementioned energy ray curable component and coloring agent, the formed film for forming an energy ray curable protective film exhibits the same color as the film for forming a thermosetting protective film described above. The same effect is obtained when the coloring agent (I) is contained.

As the above-mentioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants and general-purpose additives in the composition (IV-1), there can be mentioned the same as those in the composition (III-1). 1) Thermosetting component (B), filler (D), coupling agent (E), crosslinking agent (F), photopolymerization initiator (H), colorant (I) and general-purpose additive (J ) the same thing.

In the composition (IV-1), each of the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general-purpose additives may be used alone or in combination of two or more , and when two or more of them are used in combination, the combination and ratio of these can be arbitrarily selected.

The contents of the aforementioned thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants and general-purpose additives in the composition (IV-1) can be appropriately adjusted according to the purpose, and there is no special limited.

Since the composition (IV-1) improves workability by dilution, it is preferable to further contain a solvent. Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the above-mentioned composition (III-1). The solvent contained in composition (IV-1) may be only 1 type, or may be 2 or more types.

>>Production method of energy ray curable protective film forming composition>> Compositions for forming an energy ray curable protective film such as the composition (IV-1) can be obtained by preparing each component for constituting the composition. The order of addition of each component is not particularly limited, and two or more components may be added at the same time. When using a solvent, the solvent may be mixed with any of the prepared ingredients other than the solvent and used by diluting the prepared ingredients in advance, or may be used without pre-diluting any of the prepared ingredients other than the solvent, and the solvent may be mixed with the prepared ingredients Mixed and used. There is no particular limitation on the method of mixing the ingredients during preparation, and it can be appropriately selected from known methods such as a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing by using a mixer, and a method of mixing by applying ultrasonic waves. Can. The temperature and time of adding and mixing each component are not particularly limited as long as the ingredients are not degraded, and can be adjusted appropriately. The temperature is preferably 15~30°C.

○Films for forming non-hardening protective films The non-curable protective film-forming thin film does not show characteristic changes due to curing, and in the present invention, it is considered that a protective film is formed at the stage of being attached to the target site such as the aforementioned back surface of the semiconductor wafer.

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

>Non-hardening protective film forming composition (V-1)> As a composition for forming a non-curable protective film, for example, the composition (V-1) for forming a non-curable protective film containing the aforementioned thermoplastic resin (in this specification, there are only abbreviated as "composition (V-1) 1)", etc.

[thermoplastic resin] The aforementioned thermoplastic resin is not particularly limited. As the above-mentioned thermoplastic resin, more specifically, for example, acrylic resin, polyester, polyurethane, phenoxy resin, polybutene, The same thing as non-hardening resins such as polybutadiene and polystyrene.

The aforementioned thermoplastic resins contained in the composition (V-1) and the non-curable protective film-forming film may be only one kind, or may be two or more kinds. choose.

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

Composition (V-1) may contain, in addition to the aforementioned thermoplastic resin, one or two or more types selected from the group consisting of fillers, coupling agents, crosslinking agents, colorants, and general-purpose additives according to purposes.

For example, by using the composition (V-1) containing the aforementioned thermoplastic resin and coloring agent, the formed film for forming a non-hardening protective film and the film for forming a thermosetting protective film described above contain the coloring agent (I ) has the same effect.

As the above-mentioned filler, coupling agent, crosslinking agent, colorant and general additives in the composition (V-1), each can include the filler (D) and the coupling agent in the composition (III-1). (E), crosslinking agent (F), coloring agent (I) and general-purpose additive (J) same thing.

In the composition (V-1), each of the aforementioned fillers, coupling agents, crosslinking agents, colorants, and general-purpose additives may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination of these And the ratio can be selected arbitrarily.

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

Since the workability of the composition (V-1) improves by dilution, it is preferable to further contain a solvent. Examples of the solvent contained in the composition (V-1) include the same solvents as those 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.

>>Production method of non-curable protective film forming composition>> Non-curable protective film forming compositions such as composition (V-1) can be obtained by preparing each component to constitute the composition. The order of addition of each component is not particularly limited, and two or more components may be added at the same time. When using a solvent, the solvent may be mixed with any of the prepared ingredients other than the solvent and used by diluting the prepared ingredients in advance, or may be used without pre-diluting any of the prepared ingredients other than the solvent, and the solvent may be mixed with the prepared ingredients Mixed and used. There is no particular limitation on the method of mixing the ingredients during preparation, and it can be appropriately selected from known methods such as a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing by using a mixer, and a method of mixing by applying ultrasonic waves. Can. The temperature and time of adding and mixing each component are not particularly limited as long as the ingredients are not degraded, and can be adjusted appropriately. The temperature is preferably 15~30°C.

◎Other layers The said support sheet may be provided with other layers, such as the said intermediate|middle layer, other than a base material and an adhesive agent layer in the range which does not impair the effect of this invention. 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 within the range that does not impair the effects of the present invention. In this case, the other layers may be The aforementioned other layers provided with the support sheet may also be arranged without directly contacting the support sheet. The aforementioned other layers can be arbitrarily selected according to purposes, and the types thereof are not particularly limited.

As an embodiment of the support sheet and protective film-forming composite sheet, 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 source. The aforementioned acrylic polymer and crosslinking agent, and in the adhesive layer, the content of the crosslinking agent is 0.3 to 50 parts by mass relative to 100 parts by mass of the content of the aforementioned acrylic polymer, and the aforementioned The maximum height roughness (Rz) is 0.01~8μm.

As one embodiment of the support sheet and protective film-forming composite sheet, 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 source. The aforementioned acrylic polymer and crosslinking agent, and in the adhesive layer, the content of the crosslinking agent is 0.3 to 50 parts by mass relative to 100 parts by mass of the content of the aforementioned acrylic polymer, and the aforementioned acrylic polymer has an alkane A structural unit derived from an alkyl (meth)acrylate with a carbon number of 4 or more, and a structural unit derived from a hydroxyl-containing monomer, and the above-mentioned maximum height roughness (Rz) of the first surface of the substrate is 0.01~ 8 μm.

As an embodiment of the support sheet and protective film-forming composite sheet, 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 source. The aforementioned acrylic polymer and crosslinking agent, and in the adhesive layer, the content of the crosslinking agent is 0.3 to 50 parts by mass relative to 100 parts by mass of the content of the aforementioned acrylic polymer, and the aforementioned acrylic polymer has an alkane A structural unit derived from an alkyl (meth)acrylate having a carbon number of 4 or more, and a structural unit derived from a hydroxyl-containing monomer, and in the structural unit derived from a hydroxyl-containing monomer of the aforementioned acrylic polymer Content is 1-35 mass % with respect to the total amount of a structural unit, and the said maximum height roughness (Rz) of the 1st surface of a base material is 0.01-8 micrometers.

As an embodiment of the support sheet and protective film-forming composite sheet, 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 source. The aforementioned acrylic polymer and crosslinking agent, and in the adhesive layer, the content of the crosslinking agent is 0.3 to 50 parts by mass relative to 100 parts by mass of the content of the aforementioned acrylic polymer, and the aforementioned acrylic polymer has an alkane A structural unit derived from an alkyl (meth)acrylate having a carbon number of 4 or more, and a structural unit derived from a hydroxyl-containing monomer, and in the structural unit derived from a hydroxyl-containing monomer of the aforementioned acrylic polymer The content is 1 to 35% by mass relative to the total amount of structural units, the crosslinking agent is an isocyanate 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 protective film formation The aforementioned composite sheet for forming a protective film can be produced, for example, by a production method (in this specification, sometimes referred to as "manufacturing method (S1)") having the following steps: forming a substrate, an adhesive layer, and a protective film; The step of laminating thin films in the thickness direction in this order to form a laminated sheet (in this specification, there is a case called "laminated sheet manufacturing step (1)"); The step of storing under pressure (in this manual, there is a case called "the step of storing the laminated sheet"). The formation method of each layer (substrate, adhesive layer, and film for protective film formation) is as above-mentioned. Hereinafter, each step of the aforementioned manufacturing method (S1) will be further described in detail.

◎Manufacturing method (S1) >>Laminate manufacturing steps (1)>> In the aforementioned laminated sheet production step (1), a laminated sheet formed by laminating a base material, an adhesive layer, and a film for forming a protective film in this order in the thickness direction is manufactured. In this step, for example, by laminating the above-mentioned layers (substrate, adhesive layer, protective film forming film, etc.) in corresponding positions, a composite sheet having the same laminated structure as the target protective film forming composite sheet is manufactured. Laminates. In addition, in this specification, unless otherwise specified, "laminated sheet" means a product having the same laminated structure as the protective film-forming composite sheet as described above, and without performing the aforementioned laminated sheet storage step.

For example, when laminating an adhesive agent on a base material in the production of a support sheet, the adhesive composition described above may be applied on the base material and dried as necessary.

On the other hand, for example, when a film for forming a protective film is further laminated on the adhesive layer that has been laminated on the base material, the film for forming a protective film is directly formed by coating the composition for forming a protective film on the adhesive layer. film. The layer other than the film for protective film formation can also be laminated|stacked on the adhesive agent layer by the same method using the composition for forming this layer. In this way, when using any of the compositions to form a continuous two-layer laminated structure, the composition can be further coated on the layer formed of the aforementioned composition to form a new layer. However, among these two layers, it is preferable that the layer of the subsequent layer is formed in advance on another release film using the aforementioned composition, and by making the side of the formed layer that is in contact with the aforementioned release film the opposite side. The exposed surface is preferably bonded to the exposed surface of the remaining layer that has already been formed to form a laminated structure of two consecutive layers. In this case, it is preferable to coat the above-mentioned composition on the release-treated surface of the release film. The release film may be removed as necessary after formation of the laminated structure.

For example, a protective film-forming composite sheet is manufactured in which an adhesive layer is laminated on a substrate, and a protective film-forming film is laminated on the adhesive layer (the support sheet is a laminate of the substrate and the adhesive layer). Composite sheet for forming a protective film), the adhesive layer is laminated on the base material in advance by applying the adhesive composition on the base material and drying it as necessary, and by applying the composition for forming a protective film The product is applied on a release film, and dried as necessary to form a protective film-forming film on a release film in advance. Then, the exposed surface of the protective film-forming film was bonded to the exposed surface of the adhesive layer laminated on the substrate, and the protective film-forming film was laminated on the adhesive layer to obtain the laminated sheet.

Also, when laminating the adhesive layer on the base material, as described above, instead of applying the adhesive composition to the base material, the method of applying the adhesive composition to the release film may be applied, and the After drying, an adhesive layer is preliminarily formed on the release film, and the exposed surface of the layer is bonded to one surface of the base material to laminate the adhesive layer on the base material. In either method, the release film may be removed at any point after formation of the target laminated 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 of forming a release film in advance and sticking it to the surface of the target layer, so it is appropriately selected and used according to needs. Layers of such steps can be used to manufacture the aforementioned laminated sheet.

For example, the composite sheet for protective film formation is normally stored in the state which bonded the release film to the surface of the outermost layer (for example, the film for protective film formation) on the side opposite to a support sheet. Therefore, by applying a composition for forming a layer constituting the outermost layer, such as a protective film-forming composition, on the release film (preferably its release-treated surface), and drying it as necessary, the The layer constituting the outermost layer is preformed on the release film, and the remaining layers are laminated on the exposed surface of the layer opposite to the side in contact with the release film using any of the above methods. In the combined state, the aforementioned laminated sheet can also be obtained.

When the composite sheet for forming a protective film is equipped with the above-mentioned other layers, it may be performed by appropriately adding the above-mentioned other layers so as to obtain an appropriate arrangement position at an appropriate time point in the above-mentioned laminated sheet manufacturing step (1). .

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

>>Preservation steps of laminate>> In the step of storing the laminated sheet, the laminated sheet is stored while being pressed in its thickness direction. In this step, as a method of storing the above-mentioned laminated sheet while pressing, for example, the following method can be mentioned: the elongated aforementioned laminated sheet is wound into a roll shape, and the rolled-up laminated sheet is placed in the original state. state, the method of storing the laminated sheet while applying the pressure generated by winding to one or both sides of the laminated sheet; , or non-long strip of the aforementioned laminated sheet is stored while applying pressure to one or both sides thereof.

When the long laminated sheet is wound into a roll shape, it is preferable that the laminated sheet is wound in the longitudinal direction. When winding the laminate, for example, the winding tension is preferably 150~170N/m, the winding speed is preferably 45~55m/min, and the winding tension reduction rate (Taper ratio) is preferably 85~95%. By employing such winding conditions, the laminated sheet can be pressurized and stored at a more suitable pressure. Such winding conditions are particularly suitable for application to laminated sheets with a thickness of 100-300 μm, a width of 300-500 mm, and a length of 40-60 m, but the size of the laminated sheet is not limited thereto.

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

The laminated sheet rolled into a roll can be stored at room temperature or at room temperature, preferably while being heated. By storing under heat and pressure in this way, it is possible to obtain a composite sheet for protective film formation that is more excellent in the laminarity of the adhesive layer and the film for protective film formation, and the visibility of the protective film or the film for protective film formation through the support sheet. .

The heating temperature at the time of storage when winding up the laminated sheet into a roll shape is not particularly limited, but is preferably 53-75°C, more preferably 55-70°C, and particularly preferably 57-65°C.

The storage time when the laminated sheet is wound into a roll shape is not particularly limited, preferably 24-720 hours (1-30 days), preferably 48-480 hours (2-20 days), and 72-720 hours. 240 hours (3~10 days) is the best.

A laminated sheet wound into a roll, for example, a film for forming a protective film and a support sheet are processed into a specific shape, and a laminate of multiple sheets of the support sheet and film for forming a protective film thus processed can also be used in the The film side for protective film formation, etc. are bonded to the elongate release film, and it arrange|positions in the longitudinal direction of this release film. In this case, the thin film for forming a protective film preferably has the same or substantially the same planar shape (usually circular shape) as that of the semiconductor wafer. Also, at this time, the support sheet preferably has the same or substantially the same outer peripheral shape as the jig used to fix the support sheet in the cutting device. In addition, at this time, it is preferable that a belt-shaped sheet is arranged near the peripheral portion in the short direction of the laminated product of the release film so as not to overlap the laminated product. This sheet is used to suppress the level difference (in this specification, there is a case called "lamination marks") that occurs on the surface of the laminate when the laminate sheet is wound into a roll. The above-mentioned lamination traces are due to the fact that in the roll of the laminate sheet, the lamination position of the above-mentioned laminate (the laminate of the processed support sheet and the film for protective film formation) is not consistent in the radial direction of the roll, causing the surface of the above-mentioned laminate to bear more produced by high pressure. When the sheet is placed in the vicinity of the peripheral portion, such a high pressure is not applied to the surface of the layered product, and the generation of the layered layer marks can be suppressed.

When the elongated laminated sheet is not rolled into a roll but is in an unfolded state, and when the laminated sheet is not long, it is preferable to store a plurality of such laminated sheets by further laminating them. Furthermore, when the laminated sheets are laminated in this way, it is preferable that the directions of the laminated sheets and the positions of the peripheral portions of the plurality of laminated sheets coincide with each other.

The shape and size of the non-long laminated sheet (in other words, single laminated sheet) are not particularly limited. For example, a dicing device can be used to process a single semiconductor wafer, and the laminated sheet can be adjusted according to the shape and size of the semiconductor wafer and the shape and size of the jig for fixing the support sheet in the dicing device. Good shape and size.

The above-mentioned laminated sheet in the laminated state can also be stored at normal temperature or at room temperature, but it is better to store it while heating. In this way, by storing under heat and pressure, it is possible to use a composite for forming a protective film that is more excellent in the laminarity of the adhesive layer and the film for forming a protective film, and the visibility of the printed characters through the support sheet of the protective film or the film for forming a protective film. piece. Furthermore, both the heating temperature and the storage time when storing the laminated sheet in a laminated state under pressure can be the same as when the laminated sheet is wound into a roll shape as described above.

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

In the laminated sheet manufacturing step (1) of the manufacturing method (S1), the order of lamination (bonding) of the base material, the adhesive layer, and the protective film forming film is not particularly limited, and the support sheet is prepared in advance (preliminarily laminating the adhesive layer material), and when the film for forming a protective film is manufactured in advance and the film for forming a protective film is laminated on a support sheet, either or both of the film for forming a support sheet and the film for forming a protective film may be used alone or before lamination of these , Preserve under pressure using the same method as in the case of the above-mentioned laminated sheet. By separately storing the support sheet before lamination under pressure, it is possible to more effectively suppress the occurrence of the aforementioned non-adhesive region between the base material and the adhesive layer. In addition, by storing the film for protective film formation before lamination alone under pressure, the unevenness of the film for protective film formation and the surface (second surface) on the side of the adhesive layer of the protective film becomes smaller (the smoothness is larger). ), the film for protective film formation and the design improvement of the protective film.

That is, the above-mentioned composite sheet for forming a protective film can also be produced, for example, by a production method (in this specification, sometimes referred to as "manufacturing method (S2)") having the following steps: The film is laminated on the above-mentioned adhesive layer of the support sheet on which the substrate and the adhesive layer are laminated, and the laminated layer of the composition is formed by laminating the substrate, the adhesive layer, and the film for forming the protective film in this order in the thickness direction (in this specification, there is a case called "laminated sheet manufacturing step (2)"); and the step of storing the aforementioned laminated sheet while pressing in its thickness direction (preservation step); and further described in the aforementioned Before the laminated sheet production step (2) (i.e., before laminating the aforementioned support sheet and protective film-forming film), either or both of the aforementioned support sheet and protective film-forming film are pressurized in the thickness direction thereof. Steps of side preservation (in this specification, the step of preserving the support sheet may be referred to as the "support sheet preservation step", and the step of preserving the protective film forming film may be referred to as the "protective film forming film preservation step").

◎Manufacturing method (S2) The aforementioned manufacturing method (S2) performs the laminated sheet manufacturing step (2) as the aforementioned laminated sheet manufacturing step (1), except that either or both of the aforementioned support sheet storage step and protective film forming film storage step are additionally performed. , the same as the above-mentioned manufacturing method (S1).

>>Laminate manufacturing steps (2)>> The aforementioned laminated sheet manufacturing step (2) is as described above. The method of manufacturing the support sheet in advance, and manufacturing the film for forming the protective film in advance, and laminating the film for forming the protective film on the support sheet is the same as The same is true for the laminated sheet manufacturing step (1) of the manufacturing method (S1).

>>Support Sheet Preservation Procedure, Protective Film Formation Film Preservation Procedure>> The aforementioned support sheet storage step and protective film formation film storage step can be compared with the laminated sheet in the production method (S1) except that the object of preservation is a non-laminated sheet but a support sheet or a film for protective film formation. The saving procedure is performed in the same manner. At this time, for example, the storage time of the support sheet and the protective film forming film can be independently 24 to 720 hours (1 to 30 days), 48 to 480 hours (2 to 20 days), and And any one of 72~240 hours (3~10 days).

On the other hand, in the support sheet storage step and protective film formation film storage step, each of the storage objects is changed as described above and the storage time of the storage objects (support sheet or protective film formation film) is changed, except for these changes. Other than that, it can be carried out in the same manner as in the step of storing the laminated sheet in the manufacturing method (S1). At this time, for example, the storage time of the support sheet and the protective film forming film can be independently 12 to 720 hours (0.5 to 30 days), 12 to 480 hours (0.5 to 20 days), and 12 to 240 hours (0.5 to 20 days). 10 days). But this is an example of the aforementioned save time. Example

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

>Raw materials for the production of protective film-forming compositions> The raw materials used for manufacture of the composition for protective film formation are shown below. ‧Polymer component (A) (A)-1: Acrylic polymer obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) (weight average molecular weight 370000, glass transition temperature 6°C) ‧Thermosetting components (B1) (B1)-1: Bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184~194g/eq) (B1)-2: Bisphenol A type epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800~900g/eq) (B1)-3: Dicyclopentadiene-type epoxy resin ("Epiclon HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 255~260g/eq) ‧Thermosetting components (B2) (B2)-1: Dicyandiamide ("ADEKA HARDENER EH-3636AS" manufactured by ADEKA, thermally active latent epoxy resin hardener, active hydrogen content 21g/eq) ‧Hardening Accelerator (C) (C)-1: 2-Phenyl-4,5-Dihydroxymethylimidazole ("CUREZOLE 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.) ‧Filler (D) (D)-1: Silicon oxide filler (SC2050MA manufactured by ADMATECHS Co., Ltd., silicon oxide filler surface-modified with epoxy compounds, average particle size 0.5 μm) ‧Coupling agent (E) (E)-1: 3-Aminopropyltrimethoxysilane ("A-1110" manufactured by NUC Corporation) ‧Coloring agent (I) (I)-1: Black pigment (made by Dainichi Seika Co., Ltd.)

[Example 1] >Manufacture of support sheet> (Manufacture of Adhesive Composition (I-4)) An acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate crosslinking agent ("TAKENATE D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)) were produced, and A non-energy ray-curable adhesive composition (I-4) having a solid content concentration of 30% by mass of a mixed solvent containing methyl ethyl ketone, toluene, and ethyl acetate as a solvent. The aforesaid acrylic polymer is a prepolymer with a weight average molecular weight of 800,000 obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass). copolymer.

(manufacture of support sheet) Using a release film ("SP-PET381031" manufactured by LINTEC Co., Ltd., thickness 38 μm) after peeling one side of a polyethylene terephthalate film by silicone treatment, the adhesive composition obtained above (I-4) Apply on the peeling-treated surface, and heat at 120° C. for 2 minutes to dry to form a non-energy ray-curable adhesive layer. At this time, conditions were set so that the thickness of the adhesive layer would be 4 μm, and the adhesive composition (I-4) was applied.

A polypropylene film (manufactured by Mitsubishi Plastics Co., Ltd., thickness 80 μm) is sandwiched between a metal roll with a concave-convex surface and a metal roll with a smooth surface, and the concave-convex surface of the metal roll is heated at 60°C and rotated to press. On one surface of a polypropylene film, a base material with one side being uneven and the other side being smooth (glossy) is produced. When the R value of the base material was measured similarly to the R value of the adhesive layer about the uneven surface of this base material, it was 1.8 micrometers.

Next, by attaching the concave-convex surface of the aforementioned base material to the exposed surface of the adhesive layer obtained above, a base material, an adhesive layer, and a release film are laminated in this order in the thickness direction to form a support. piece. The width of the obtained support sheet (in other words, the width of the base material and the adhesive layer) was 400 mm, and the length was 250 m. The support sheet of this invention was obtained as mentioned above.

Next, with respect to this support sheet, the evaluation regarding the non-bonding area between the base material and the adhesive layer mentioned later was performed immediately. Moreover, this support sheet was used as it is for manufacture of the composite sheet for protective film formation mentioned later as it is.

>Manufacture of composite sheet for protective film formation> (Manufacture of protective film forming composition (III-1)) Make polymer component (A)-1 (150 mass parts), thermosetting component (B1)-1 (60 mass parts), (B1)-2 (10 mass parts), (B1)-3 (30 mass parts ), (B2)-1 (2 mass parts), hardening accelerator (C)-1 (2 mass parts), filler (D)-1 (320 mass parts), coupling agent (E)-1 (2 mass parts parts), and coloring agent (I)-1 (18 parts by mass) were dissolved or dispersed in a mixed solvent of methyl ethyl ketone, toluene and ethyl acetate, and a solid content concentration of 51% by mass was obtained by stirring at 23°C. Thermosetting protective film forming composition (III-1). In addition, all the compounding quantities shown here are solid content quantities.

(Manufacture of film for protective film formation) The above-obtained composition for forming a protective film (III-1) was coated with a doctor blade coater on a release film treated with silicone on one side of a polyethylene terephthalate film (No. 2 Release film, "SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm) The aforementioned release treatment surface was dried at 100° C. for 2 minutes to produce a film for forming a thermosetting protective film with a thickness of 25 μm.

Then, by attaching the release-treated surface of the release film (the first release film, "SP-PET381031" manufactured by LINTEC Corporation, thickness 38 μm) to the side of the obtained film for forming a protective film that does not have the second release film, The exposed surface was obtained to obtain a laminated film having a first release film on one surface of the film for forming a protective film and a second release film on the other surface. The width of the obtained laminated film (in other words, the width of the film for protective film formation, the 1st release film, and the 2nd release film) was 400 mm.

(Manufacture of composite sheets for protective film formation) One set (two pieces) of rollers having a diameter of 5 cm and a region from the surface to a depth of 3 mm made of heat-resistant silicone rubber with a hardness of 50 degrees was prepared. The release film was removed from the support sheet adhesive layer obtained above. Also, the first release film was removed from the laminated film obtained above. Next, the exposed surface of the adhesive layer produced by removing the above-mentioned release film and the exposed surface of the protective film-forming film produced by removing the above-mentioned first release film face each other, and these support sheets and the protective film-forming film are laminated. While becoming a laminate, the laminate is heated and pressed under a pressure of 0.5 MPa by passing the laminate at a speed of 0.3 m/min through the gap between the rollers whose temperature is set at 60°C (heat bonding ). In this way, a laminated sheet having the same laminated structure as the target protective film forming composite sheet is produced by laminating the base material, the adhesive layer, the protective film forming film, and the second release film in the thickness direction in this order. (Composite sheet for protective film formation before storage). The obtained laminated sheet had a width (in other words, the width of the supporting sheet) of 400 mm.

Next, take the laminated sheet obtained above with an overall size of 400mm x 250m, take its longitudinal direction as the take-up direction, and set a take-up tension of 160N/m, a take-up speed of 50m/min, and a take-up tension reduction rate of 90%. Under the condition, the core material of ABS resin is wound and coiled into a roll shape. At this time, the laminated sheet was wound up with the base material facing outward in the radial direction of the roll (in other words, the second release film was brought into contact with the core material). Next, this roll-shaped laminated sheet was left to stand for 7 days (168 hours) under the temperature conditions of 60° C. in an air environment. As above, the composite sheet for protective film formation of this invention which has the structure shown in FIG. 2 is obtained.

Next, after finishing storage under such heating and pressurizing conditions, the following items were evaluated about the composite sheet for protective film formation of this invention.

>Evaluation of support sheet and composite sheet for protective film formation> (Measurement of R value of adhesive layer) A test piece having a size of 3 mm×3 mm was cut out from five composite sheets for forming a protective film obtained above. Among the circular film for forming a protective film, the five cutting positions corresponded to one center portion, and four positions corresponded to approximately point-symmetrical positions near the peripheral portion with respect to the center portion. Among these 5 cutting positions, the distance between the center of one position corresponding to the central part and the other 4 positions close to the peripheral part was 100 mm.

Using a cross-sectional material manufacturing device ("CROSS SECTION POLISHER-SM-09010" manufactured by JEOL Corporation), set the condition of the intermittent switch to "in" for 10 seconds, "out" to 5 seconds, and the voltage of the ion source to 3 kV, the total polishing time was set to 24 hours, and the cross section was formed from the aforementioned test piece. The newly formed cross section was set to have only one side per one test piece.

Using a scanning electron microscope (SEM), observe the newly formed cross-sections of these five test pieces. For each test piece, the (sum of the straight-line distances between adjacent meaningful vertices)/(total of the adhesive layer The agent layer is the ratio of the linear distance in the horizontal direction). At this time, the observation area of the cross section of the test piece was set to a region of 1 mm in the width direction of the cross section. And, the average value of this ratio was adopted as the R value of the adhesive layer. The results are shown in Table 1. Also, the method of measuring and obtaining the R value of the substrate is the same as the method of measuring and obtaining the R value of the adhesive layer.

(Evaluation of print visibility of protective film) From the composite sheet for forming a protective film obtained above, the second release film was removed, and the exposed surface (the surface opposite to the adhesive layer side) of the film for forming a protective film thus produced was attached to an 8-inch inch semiconductor wafer backside. The attachment at this time was performed using a tape mounter ("RAD2700" manufactured by Lintec Corporation). Thereby, the first laminated structure formed by laminating the base material, the adhesive layer, the thin film for forming a protective film, and the semiconductor wafer in the thickness direction in this order is produced.

Next, using a laser printing device (“CSM300M” manufactured by EO Technics Co., Ltd.), the surface (second surface) on the side of the adhesive layer of the film for forming a protective film in the first laminated structure was printed by passing through the support sheet. Printing is performed by irradiating laser light. At this time, printing was performed to form characters with a size of 0.3 mm×0.2 mm.

Next, the printing (laser printing) of this film for protective film formation was observed visually through a support sheet, and the visibility of printing (character) was evaluated based on the following reference|standard. The results are shown in Table 1. The print visibility of the protective film-forming film evaluated here can be considered to be equivalent to the print visibility of the protective film. A: Printed characters are vivid and can be easily seen. B: Printed characters are slightly blurred and cannot be easily recognized. C: Printed characters are unclear and cannot be recognized.

Next, the support sheet (base material and adhesive layer) is peeled off from this film for protective film formation. Next, the thickness of the lines of the printed characters (characters) formed on the film for protective film formation was measured using an optical microscope. As a result, the thickness of the line was 40 μm or more, and it was possible to print clearly.

(Evaluation of Adhesion between Substrate and Adhesive Layer) According to JIS K5600-5-6, after cutting the adhesive layer of the support sheet into 100 grids of 1mm square with a rotary cutter and pressing the adhesive tape (CELLO-TAPE) [manufactured by NICHIBAN Corporation, registered trademark]), the When the adhesive tape is peeled off at an angle of about 60° for 0.5 seconds to 1.0 seconds, the adhesion between the base material and the adhesive layer is tested by calculating the number of remaining cells in 100 cells. Adhesion evaluation was performed based on the following determination criteria. And the evaluation about the adhesiveness of a base material and an adhesive layer was performed based on the following reference|standard. The results are shown in Table 1. A: The number of remaining grids is 90 or more. B: The number of remaining grids is 70 or more and less than 90. C: The number of remaining grids is less than 70.

>Manufacture of support sheet and protective film forming composite sheet and evaluation of support sheet and protective film forming composite sheet> [Example 2] In Example 1, except that the concave-convex surface of the metal roll was rotated while heating at 60°C to press one surface of a polypropylene film (manufactured by Mitsubishi Plastics Co., Ltd., thickness 80 μm), the metal roll with the concave-convex surface and Except that the gap between metal rollers with smooth surfaces is adjusted to be narrower than in Example 1, the same method as in Example 1 was used to manufacture a base material with one side having an uneven surface and the other side being a smooth surface (glossy surface) . When the R value of the substrate was measured with respect to the uneven surface of the substrate, it was 2.8. Except for the point of using this base material, the support sheet was produced and evaluated using the same method as in Example 1. And the composite sheet for protective film formation was produced and evaluated by the same method as in Example 1 except the point which used such a support sheet. The results are shown in Table 1.

[Example 3] In Example 2, except that the concave-convex surface of the metal roll was rotated while heating at 60° C. to press one surface of a polypropylene film (manufactured by Mitsubishi Plastics Co., Ltd., thickness 80 μm), the metal roll with the concave-convex surface and Except that the gap between metal rollers with smooth surfaces is adjusted to be narrower than that of Example 2, the same method as in Example 2 was used to manufacture a base material with one side having an uneven surface and the other side being a smooth surface (glossy surface) . When the R value of the substrate was measured with respect to the uneven surface of the substrate, it was 3.7. Except for the point of using this base material, the support sheet was produced and evaluated using the same method as in Example 1. And the composite sheet for protective film formation was produced and evaluated by the same method as in Example 1 except the point which used such a support sheet. The results are shown in Table 1.

[Comparative example 1] In Example 1, except that the concave-convex surface of the metal roll was rotated while heating at 60°C to press one surface of a polypropylene film (manufactured by Mitsubishi Plastics Co., Ltd., thickness 80 μm), the metal roll with the concave-convex surface and Except that the gap between metal rollers with smooth surfaces is adjusted to be wider than in Example 1, the same method as in Example 1 was used to manufacture a base material with one side having an uneven surface and the other side being a smooth surface (glossy surface) . When the R value of the substrate was measured with respect to the uneven surface of the substrate, it was 1.0. Except for the point of using this base material, the support sheet was produced and evaluated using the same method as in Example 1. And the composite sheet for protective film formation was produced and evaluated by the same method as in Example 1 except the point which used such a support sheet. The results are shown in Table 1.

[Comparative example 2] In Example 3, except that the concave-convex surface of the metal roll was rotated while heating at 60° C. to press one surface of a polypropylene film (manufactured by Mitsubishi Plastics Co., Ltd., thickness 80 μm), the metal roll with the concave-convex surface and Except that the gap between metal rollers with smooth surfaces is adjusted to be narrower than in Example 3, a base material with one side having an uneven surface and the other side being a smooth (glossy) surface was manufactured using the same method as in Example 3. . When the R value of the substrate was measured with respect to the uneven surface of the substrate, it was 5.7. Except for the point of using this base material, the support sheet was produced and evaluated using the same method as in Example 1. And the composite sheet for protective film formation was produced and evaluated by the same method as in Example 1 except the point which used such a support sheet.

And the composite sheet for protective film formation was produced and evaluated by the same method as in Example 1 except the point which used such a support sheet. The results are shown in Table 1.

Table 1

It is clear from the above results that in Examples 1 to 3, the R value of the adhesive layer is 2 or more (2 to 4), and the adhesion between the base material and the adhesive is particularly excellent. Moreover, in these embodiments, the R value of the aforementioned adhesive layer is less than 5.0 (2-4). The protective film and the film for forming a protective film are particularly excellent in the visibility of printed characters through the support sheet.

On the other hand, in Comparative Example 1, the R value of the adhesive layer was 1.2, the adhesiveness between the base material and the adhesive was insufficient, and a non-bonding region existed between the base material and the adhesive.

Also, in Comparative Example 2, the R value of the adhesive layer was 6.0, and the adhesive layer had a very thick region. Therefore, the visibility of printed characters through the protective film (film for forming a protective film) of the support sheet is poor. Industrial availability

The present invention can be utilized in the manufacture of semiconductor devices.

1A, 1B, 1C‧‧‧Composite sheet for protective film formation 10‧‧‧Support sheet 10a‧‧‧Surface of the protective film forming film side (first surface) of the support sheet 10b‧‧‧Second surface of the support sheet 11‧‧‧Substrate 11a‧‧‧Surface on the side of the adhesive layer of the substrate (first surface, uneven surface) 11b‧‧‧Second surface of the substrate 11 12‧‧‧Adhesive layer 12a‧‧‧adhesion The surface (first surface) of the agent layer opposite to the substrate side 12b‧‧‧the substrate side surface (second surface) of the adhesive layer 13, 23 Protective film forming film 13a‧‧‧protective film formation The surface 13b of the film opposite to the adhesive layer side ‧‧‧the adhesive layer side (second surface) of the film for protective film formation 15‧‧‧peeling film 16‧‧‧adhesive layer for jigs 16a‧‧‧adhesive layer upper surface and side surface for jig 23a‧‧‧surface of protective film forming film not in contact with adhesive layer 23b‧‧‧surfaces 91, 92 of adhesive layer side of protective film forming film ‧‧‧Non-bonding area L _a1 , L _b1 , L _a2 , L _b2 ‧‧‧The straight-line distance L ₁ , L ₂ between adjacent meaningful vertices ‧‧‧Projected on the horizontal direction of the adhesive layer Line segment T a of plane T _a ‧‧‧thickness of adhesive layer T _a1 ‧‧‧minimum value of adhesive layer thickness T _a2 ‧‧‧maximum value of adhesive layer thickness T _p ‧‧‧thickness of protective film forming film thickness

Fig. 1 schematically shows a cross-sectional view of a support sheet and a composite sheet for forming a protective film according to an embodiment of the present invention. Fig. 2 schematically shows a cross-sectional view of a composite sheet for forming a protective film and a support sheet according to an embodiment of the present invention. Fig. 3 schematically shows a cross-sectional view of a composite sheet for forming a protective film and a support sheet according to an embodiment of the present invention. Fig. 4 is an enlarged cross-sectional view of the supporting sheet and the composite sheet for forming a protective film shown in Fig. 1 . Fig. 5 is an enlarged cross-sectional view of the supporting sheet and the composite sheet for forming a protective film shown in Fig. 1 .

1A‧‧‧Composite sheet for protective film formation

10‧‧‧Support piece

10a‧‧‧The surface of the protective film forming film side of the support sheet (1st surface)

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

11‧‧‧Substrate

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

11b‧‧‧The second surface of the substrate 11

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

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

12‧‧‧adhesive layer

13‧‧‧Film for protective film formation

13a‧‧‧The surface of the film for forming a protective film that is opposite to the side of the adhesive layer

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

15‧‧‧Peeling film

16‧‧‧adhesive layer for jig

16a‧‧‧The upper surface and side of the adhesive layer for jigs

Claims (3)

A support sheet is provided with a base material, and the support sheet is provided with an adhesive layer on the aforementioned base material, The surface of the aforementioned substrate on the side of the aforementioned adhesive layer is a concave-convex surface, Cut test pieces from 5 places of the aforementioned support sheet, and observe the cross-section of the aforementioned adhesive layer on these 5 test pieces, (the sum of the straight-line distances between adjacent meaningful vertices)/(horizontal to the adhesive layer The average value of the ratio of the linear distance in the direction) is 1.5 or more and less than 5.0. The supporting sheet as described in claim 1 of the patent application, wherein the aforementioned adhesive layer is in direct contact with the concave-convex surface of the aforementioned substrate. A composite sheet for forming a protective film comprising a thin film for forming a protective film on the adhesive layer in the support sheet as described in claim 1 or 2 of the patent application.

Images