JP6776081B2 - Manufacturing method of semiconductor chip with protective film and manufacturing method of semiconductor device - Google Patents

Description

The present invention relates to a method for manufacturing a semiconductor chip with a protective film and a method for manufacturing a semiconductor device.

In recent years, semiconductor devices to which a mounting method called a so-called face down method has been applied have been manufactured. In the face-down method, a semiconductor chip having an electrode such as a bump on the circuit surface is used, and the electrode is bonded to the substrate. Therefore, the back surface of the semiconductor chip opposite to the circuit forming surface may be exposed.

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

In order to form such a protective film, for example, a protective film forming film configured to form a protective film by curing is used, and usually, the protective film forming film is provided on a support sheet. , Used as a composite sheet for forming a protective film. In the composite sheet for forming a protective film, the protective film forming film can form a protective film by curing, and the support sheet can be used as a dicing sheet, so that the protective film forming film and the dicing sheet are integrated. It is possible to assume that it has been done. As a protective film forming film, a thermosetting film, that is, a film forming a protective film by thermosetting is known.

FIG. 5 is a cross-sectional view for schematically explaining a method for manufacturing a semiconductor chip with a protective film when a thermosetting film for forming a protective film is used.
In this manufacturing method, first, as shown in FIG. 5A, the semiconductor wafer 8'in which the modified layer 81'is formed in advance is formed on the protective film forming film 931 of the protective film forming composite sheet 901. It is provided on the top. The protective film forming composite sheet 901 is a protective film forming film 931 provided on the support sheet 10. Next, as shown in FIG. 5B, the protective film forming film 931 is cured by heating to obtain a protective film 931'. Next, the semiconductor wafer 8'is expanded together with the protective film forming composite sheet 901'after forming the protective film 931'in the surface direction of the protective film 931'(the direction indicated by the arrow I in the figure). As shown in 5 (c), a plurality of semiconductor chips 8 with protective films are obtained by cutting the protective film 931'and dividing the semiconductor wafer 8'at the site of the modified layer 81'. In FIG. 5, reference numeral 9310'indicates the protective film after cutting.
As shown here, a method of forming a modified layer inside a semiconductor wafer and dividing the semiconductor wafer at a portion of the modified layer is a method of forming a semiconductor wafer by conventional blade dicing or the like, as will be described later. It has an advantage over the dividing method, and its widespread use is desired.

However, in this manufacturing method, in order to thermoset the protective film forming film 931 in the process of obtaining the semiconductor chip 8 with a protective film, a support sheet 10 having heat resistance is required, and for that purpose, a support sheet 10 is required. It is necessary to increase the elastic modulus of the sheet 10. Here, as the support sheet 10, the adhesive layer 12 is provided on the base material 11, and in this case, it is necessary to particularly increase the elastic modulus of the base material 11. However, if the elastic modulus of the support sheet 10 is high, the support sheet 10 (composite sheet 901'for forming a protective film) is difficult to expand, so that the protective film 931'cannot be sufficiently cut.
Further, when the protective film 931 is heat-cured, the protective film 931'shrinks due to curing, and division proceeds ahead of at least a part of the semiconductor wafer 8'(not shown). The supportability on the support sheet 10 is lowered, and slack is likely to occur.

On the other hand, as a method of obtaining a semiconductor chip by dividing a semiconductor wafer, a method in which the protective film forming film is not cured in the process of obtaining the semiconductor chip is also conceivable. In this method, not a semiconductor chip with a protective film but a semiconductor chip with a film for forming a protective film is manufactured. Even in such a case, the protective film forming film is usually provided on the support sheet and used in the state of the protective film forming composite sheet.
FIG. 6 is a cross-sectional view for schematically explaining a method for manufacturing such a semiconductor chip with a protective film-forming film.

In this manufacturing method, first, as shown in FIG. 6A, the semiconductor wafer 8'in which the modified layer 81'is formed in advance is protected by the composite sheet 902 for forming the protective film, as described above. It is provided on the film forming film 932. The protective film forming composite sheet 902 is obtained by providing the protective film forming film 932 on the support sheet 10. Next, the semiconductor wafer 8'was expanded together with the protective film forming composite sheet 902 in the surface direction of the protective film forming film 932 (the direction indicated by the arrow I in the figure) without curing the protective film forming film 932. As shown in FIG. 6B, a plurality of protective films are formed by cutting the uncured protective film forming film 932 and dividing the semiconductor wafer 8'at the site of the modified layer 81'. A semiconductor chip 8 with a film for use is obtained. In FIG. 6, reference numeral 9320 indicates a protective film forming film after cutting. In this production method, the protective film forming film 932 may be either a curable type or a non-curable type, and when it is a curable type, it may be, for example, either thermosetting or energy ray curable. Although it may be present, a curable protective film forming film is used without being cured.

In this manufacturing method, since the protective film forming film 932 is not cured, a heating step is not required, and a heat-resistant support sheet 10 is not required, and the elastic modulus of the support sheet 10 as described above can be obtained. The problem associated with the increase can be avoided, and the supportability of the semiconductor wafer 8'on the support sheet 10 does not decrease.
A method of cutting a resin film containing an organic material without curing, such as this protective film forming film, is disclosed in the case where a die bond film is used as the resin film to be attached to a semiconductor wafer (Patent Document 1). reference).

Japanese Unexamined Patent Publication No. 2011-171588

However, as described above, when the protective film forming film is cut without being cured and the semiconductor wafer is divided, the protective film forming film is not yet obtained in the obtained semiconductor chip with the protective film forming film. The elastic modulus is low because it is cured. As a result, when the semiconductor chip with the protective film-forming film is pushed up by the pins to be separated from the support sheet and picked up according to the conventional method, the push-up marks by the pins are likely to remain on the protective film-forming film. It should be noted that such a push-up mark by the pin may remain even in a protective film having a low elastic modulus. From this point of view, it is desirable that the semiconductor chip has a protective film that is sufficiently cured at the time of pickup.

Therefore, the present invention is a method for manufacturing a semiconductor chip with a protective film, which is formed by curing a protective film forming film and has a protective film cut at a target location on the back surface of the semiconductor chip, and is an expanded protective film. Alternatively, when the cutability of the protective film forming film and the supportability of the semiconductor wafer on the support sheet used at the time of expansion are good, and the semiconductor chip with the protective film is pulled away from the support sheet by pushing up with a pin, It is an object of the present invention to provide a method for manufacturing a semiconductor chip with a protective film, which can suppress the residual of a push-up mark due to a pin on the protective film.

In order to solve the above problems, the first aspect of the present invention comprises providing an energy ray-curable protective film forming film on a support sheet and providing a semiconductor wafer on the protective film forming film. After the laminated structure forming step of forming a laminated structure in which a modified layer is formed inside the semiconductor wafer and the laminated structure forming step, the protective film forming film is protected by irradiating energy rays. The protective film forming step of forming the film and the laminated structure after forming the protective film are expanded toward the surface of the protective film to cut the protective film and the semiconductor at the site of the modified layer. It has an expanding step of dividing a wafer to obtain a plurality of semiconductor chips with a protective film, and the protective film-forming film has an energy ray-curable group and a polymer (a2) having a molecular weight of 100 to 80,000. , A polymer (b) having no energy ray-curable group and a filler (d), and the compound (a2) is an acrylate-based compound having a (meth) acryloyl group as the energy ray-curable group. It is a compound, the polymer (b) is an acrylic polymer, and the total content of the compound (a2) and the polymer (b) of the protective film forming film is 15 to 70% by mass. The content of the filler (d) in the protective film-forming film is 7 to 78% by mass, and in the expanding step, the laminated structure is expanded at room temperature or while heating the protective film. To provide a method for manufacturing a semiconductor chip with a protective film.
Further, in the second aspect of the present invention, an energy ray-curable protective film forming film is provided on the support sheet, and a semiconductor wafer is provided on the protective film forming film, and the inside of the semiconductor wafer is provided. After the laminated structure forming step of forming the laminated structure in which the modified layer is formed and the laminated structure forming step, the laminated structure is expanded toward the surface of the protective film forming film. An expanding step of cutting the protective film forming film and dividing the semiconductor wafer at the site of the modified layer to obtain a plurality of semiconductor chips, and irradiating the cut protective film forming film with energy rays. It has a protective film forming step of obtaining a semiconductor chip with a protective film by forming a protective film, or forming a protective film by irradiating the protective film forming film with energy rays to form a protective film. In the step, the laminated structure after forming the protective film is expanded toward the surface of the protective film to cut the protective film, and at the site of the modified layer, the semiconductor wafer is divided into a plurality of parts. It has an expanding step of obtaining a semiconductor chip with a protective film, and the support sheet has an adhesive layer provided on a base material, and has a length of 22 mm in the CD direction and a length in the MD direction. For a 110 mm test piece of the base material, the test piece is suspended at one of both ends in the MD direction, and a load of 0.1 g / mm is applied to the other, under the conditions of 130 ° C. and 30% RH. When the test piece was heated for 2 hours and cooled to 23 ° C., the expansion / contraction rate of the test piece in the MD direction was 100 to 250%, the length in the MD direction was 22 mm, and the length in the CD direction was 110 mm. With respect to the test piece of the base material, the test piece was suspended at one of both ends in the CD direction, and a load of 0.1 g / mm was applied to the other, under the conditions of 130 ° C. and 30% RH. When the test piece was heated for 2 hours and cooled to 23 ° C., the expansion / contraction rate of the test piece in the CD direction became 100 to 150%, and for the test piece of the base material having a size of 15 mm × 140 mm, JIS K7127: Provided is a method for manufacturing a semiconductor chip with a protective film, wherein when the tensile elasticity at 23 ° C. is measured in accordance with 1999, the tensile elasticity of the test piece in both the MD direction and the CD direction is 100 to 400 MPa. ..

The method for producing a semiconductor chip with a protective film according to the first aspect and the second aspect of the present invention is a semiconductor wafer before the step of forming the laminated structure and further before the film for forming the protective film is provided. On the other hand, it is preferable to have a modified layer forming step of irradiating a laser beam so as to focus on the focal point set inside the semiconductor wafer to form the modified layer inside the semiconductor wafer.
In the method for producing a semiconductor chip with a protective film according to the first aspect and the second aspect of the present invention , the support sheet has an adhesive layer provided on a base material, and the adhesive layer is provided. It is preferable that the protective film forming film is provided in direct contact with the above.
Further, in the third aspect of the present invention , the semiconductor chip with a protective film is obtained after obtaining the semiconductor chip with a protective film by the method for manufacturing a semiconductor chip with a protective film according to the first aspect or the second aspect. Provided is a method for manufacturing a semiconductor device, which comprises a pulling step of pulling away from the support sheet.

According to the present invention, it is a method for manufacturing a semiconductor chip with a protective film, which is formed by curing a protective film forming film and has a protective film cut at a target location on the back surface of the semiconductor chip, and is protected by expansion. The cutability of the film or the film for forming the protective film and the supportability of the semiconductor wafer on the support sheet used at the time of expansion are good, and when the semiconductor chip with the protective film is pulled away from the support sheet by pushing up with a pin. Provided is a method for manufacturing a semiconductor chip with a protective film, which can suppress the residual of a push-up mark due to a pin on the protective film.

It is sectional drawing for schematically explaining one Embodiment of the manufacturing method of this invention. It is sectional drawing which shows typically the semiconductor wafer which the back grind tape is attached. It is sectional drawing for schematically explaining another embodiment of the manufacturing method of this invention. It is sectional drawing for schematically explaining one Embodiment of the pulling-off process in the manufacturing method of the semiconductor device of this invention. It is sectional drawing for schematically explaining the manufacturing method of the conventional semiconductor chip with a protective film when the composite sheet for forming a protective film provided with the thermosetting film for forming a protective film is used. It is sectional drawing for schematically explaining the manufacturing method of the conventional semiconductor chip with a protective film forming film when the composite sheet for forming a protective film provided with the non-curable protective film forming film is used.

In the method for manufacturing a semiconductor chip with a protective film of the present invention, an energy ray-curable protective film forming film is provided on a support sheet, and a semiconductor wafer is provided on the protective film forming film. After the step of forming the laminated structure for forming the laminated structure in which the modified layer is formed and the step of forming the laminated structure,
The laminated structure is expanded toward the surface of the protective film forming film to cut the protective film forming film, and the semiconductor wafer is divided at the site of the modified layer to form a plurality of semiconductor chips. It has an expanding step of obtaining and a protective film forming step of obtaining a semiconductor chip with a protective film by irradiating the protective film forming film after cutting with energy rays to form a protective film (this method is described in the present specification). In the book, it may be referred to as "manufacturing method (1)") or
A protective film forming step of irradiating the protective film forming film with energy rays to form a protective film, and expanding the laminated structure after forming the protective film toward the surface of the protective film to form the protective film. The semiconductor wafer is divided at the site of the modified layer to obtain a plurality of semiconductor chips with protective films, and the present method is described in the present specification as “Manufacturing method (2)). May be called).
In the production method (1) and the production method (2) of the present invention, the order of expanding and forming the protective film is different from each other.
Hereinafter, the method for manufacturing the semiconductor chip with a protective film of the present invention will be described in detail for each manufacturing method.

◎ Manufacturing method of semiconductor chip with protective film (Manufacturing method (1))
In the method for manufacturing a semiconductor chip with a protective film of the present invention (manufacturing method (1)), an energy ray-curable protective film forming film is provided on a support sheet, and a semiconductor wafer is provided on the protective film forming film. The step of forming a laminated structure for forming a laminated structure in which a modified layer is formed inside the semiconductor wafer, and the step of expanding the laminated structure toward the surface of the protective film forming film. In addition to cutting the protective film forming film, the semiconductor wafer is divided at the site of the modified layer to obtain a plurality of semiconductor chips, and an energy ray is applied to the protective film forming film after cutting. It has a protective film forming step of obtaining a semiconductor chip with a protective film by irradiating and forming a protective film.

According to the manufacturing method (1) of the present invention, since the protective film forming film is energy ray-curable, heating is not required to form the protective film, the support sheet does not have heat resistance, and the elastic modulus is low. You can use things. Therefore, the support sheet can be easily expanded and the protective film forming film can be sufficiently cut. Further, since heating is not required to form the protective film, a decrease in supportability (generation of slack) on the support sheet of the semiconductor wafer is suppressed.

Further, according to the manufacturing method (1) of the present invention, in the laminated structure forming step, as will be described later, a semiconductor wafer on which a modified layer has been formed in advance is provided on the protective film forming film and the support sheet. It is possible. In this case, it is not necessary to irradiate the semiconductor wafer with laser light by transmitting the support sheet and the protective film forming film in order to form the modified layer, and the types of the support sheet and the protective film forming film that can be used are There is no limitation. Further, in order to increase the transmission of laser light, the smoothness of the outermost surface layer (for example, the exposed surface of the base material) on the side opposite to the side where the protective film forming film of the support sheet is provided is improved. Since it is not necessary to make the support sheet, it is possible to suppress the occurrence of blocking during storage of the support sheet.

On the other hand, in the method of dividing a semiconductor wafer by blade dicing or the like, which has been widely used in the past, for example, since a part of the semiconductor wafer is scraped off, the semiconductor wafer is lost by the scraped amount, and the semiconductor obtained from one semiconductor wafer The number of chips is reduced. On the other hand, in the manufacturing method (1) of the present invention, the method of dividing the semiconductor wafer at the site of the modified layer avoids the above-mentioned problems because a part of the semiconductor wafer is not scraped off. It is advantageous in that it can be done.

In this specification, in order to distinguish the expanding step and the protective film forming step in the manufacturing method (1) from the expanding step and the protective film forming step in the manufacturing method (2) described later, each of them is an expanding step. (E1) may be referred to as a protective film forming step (C1). The expanding step and the protective film forming step in the manufacturing method (2) may be referred to as an expanding step (E2) and a protective film forming step (C2), respectively.

Further, in the present specification, the "back surface" of the semiconductor wafer and the semiconductor chip means "the surface opposite to the surface (circuit surface) on which the circuit is formed" of the semiconductor wafer and the semiconductor chip. Further, the "semiconductor chip with a protective film" means a "semiconductor chip having a protective film after cutting on the back surface".
Hereinafter, the manufacturing method (1) will be described in detail with reference to the drawings. The composition and constituent materials of each component described below will be described in detail separately.

FIG. 1 is a cross-sectional view for schematically explaining an embodiment of the manufacturing method (1) of the present invention. In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged for convenience, and the dimensional ratio of each component is the same as the actual one. Is not always the case.

○ Laminated structure forming step In the laminated structure forming step of the manufacturing method (1), as shown in FIG. 1A, an energy ray-curable protective film forming film 13 is provided on the support sheet 10. The semiconductor wafer 8'is provided on the protective film forming film 13, and the laminated structure 101 in which the modified layer 81'is formed is formed inside the semiconductor wafer 8'.

The support sheet 10 shown here has an adhesive layer 12 provided on the base material 11, the protective film forming film 13 is provided in direct contact with the adhesive layer 12, and the semiconductor wafer 8'is protected. It is provided in direct contact with the film forming film 13.
That is, more specifically, in the laminated structure 101, the pressure-sensitive adhesive layer 12 is provided on one surface 11a of the base material 11, and the protective film forming film 13 is provided on one surface 12a of the pressure-sensitive adhesive layer 12. The semiconductor wafer 8'is provided on one surface 13a of the protective film forming film 13. The protective film forming film 13 is an uncut film.

One surface 8a'of the semiconductor wafer 8'is a circuit forming surface, and the back surface 8b', which is a surface opposite to the circuit forming surface 8a', can be a ground surface formed by grinding as described later.

The base material 11 may be composed of one layer (single layer) or may be composed of two or more layers. When the base material 11 is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

In the present specification, not only in the case of the base material 11, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers may be different". It may be different, and only some layers may be the same. ”Furthermore,“ a plurality of layers are different from each other ”means“ at least one of the constituent materials and the thickness of each layer is different from each other ”. Means that.

The thickness of the base material is preferably 50 to 300 μm, more preferably 60 to 100 μm. When the thickness of the base material 11 is within such a range, the flexibility of the support sheet 10 (composite sheet for forming a protective film described later) and the stickability to the semiconductor wafer 8'or the semiconductor chip 8 described later are improved. Improve more.
In the present specification, the "thickness of the base material" means the thickness of the entire base material, and for example, the thickness of the base material composed of a plurality of layers is the total thickness of all the layers constituting the base material. Means

In order to improve the adhesion of the base material 11 to the layer provided on the base material (here, for example, the pressure-sensitive adhesive layer 12), the base material 11 is subjected to an unevenness treatment such as sandblasting treatment and solvent treatment, a corona discharge treatment, and an electron beam. The surface 11a may be subjected to oxidation treatment such as irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
Further, the base material 11 may have a surface 11a subjected to a primer treatment.
Further, the base material 11 prevents the base material 11 from adhering to other sheets and the base material 11 from adhering to the adsorption table when the antistatic coat layer and the semiconductor processing sheet are laminated and stored. It may have a layer or the like.

The optical properties of the base material 11 are not particularly limited as long as the effects of the present invention are not impaired, but the base material 11 is preferably one that transmits laser light or energy rays.

The base material 11 preferably has high flexibility. By using such a base material 11, the elastic modulus of the support sheet 10 becomes low, expansion becomes easy, and it is advantageous to sufficiently cut the protective film forming film. Further, when the elastic modulus of the support sheet 10 is low, as will be described later in the examples, the slack generated in the support sheet by the expanding step is eliminated by heating after the expanding step, and the restorability of the support sheet is good. Heat shrinkability) is shown.

From this point of view, the base material 11 has a stretch ratio in the MD (Machine Direction) direction of 50 to 300% and a stretch ratio in the CD (Cross Direction) direction measured by the method described in Examples described later. Is preferably 50 to 300%, and more preferably 100 to 250% in the MD direction and 100 to 150% in the CD direction.
In the present specification, the "MD direction" means the production line direction of the base material 11, and the "CD direction" means the direction orthogonal to the MD direction, that is, the width direction of the production of the base material 11. means.

Further, since the base material 11 has high flexibility, it becomes easier to pick up a semiconductor chip with a protective film, which will be described later. From this point of view, the base material 11 preferably has a tensile elastic modulus in both the MD direction and the CD direction at 23 ° C., which is measured by the method described in Examples described later, at 50 to 500 MPa, and both are 100 to 100. It is more preferably 400 MPa.

The base material 11 can be produced by a known method. For example, the resin-containing base material 11 can be produced by molding a resin composition containing the resin.

The pressure-sensitive adhesive layer 12 may be either energy ray-curable or non-energy ray-curable. The energy ray-curable pressure-sensitive adhesive layer can easily adjust the physical properties before and after curing.

The pressure-sensitive adhesive layer 12 may be composed of one layer (single layer) or may be composed of two or more layers. When the pressure-sensitive adhesive layer 12 is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the pressure-sensitive adhesive layer 12 can be appropriately selected depending on the intended purpose, but is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
In the present specification, the "thickness of the pressure-sensitive adhesive layer" means the thickness of the entire pressure-sensitive adhesive layer, and for example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers means all the layers constituting the pressure-sensitive adhesive layer. Means the total thickness of.

The optical properties of the pressure-sensitive adhesive layer 12 are not particularly limited as long as the effects of the present invention are not impaired, but the pressure-sensitive adhesive layer 12 preferably transmits laser light or energy rays.

The pressure-sensitive adhesive layer 12 can be formed by using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive described later.

The protective film forming film 13 is energy ray curable.
In the present specification, the "energy beam" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, and electron beams.
Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray curable" means the property of being cured by irradiating with energy rays, and "non-energy ray curable" means the property of not being cured by irradiating with energy rays. To do.

The protective film forming film 13 may be composed of one layer (single layer) or may be composed of two or more layers. When the protective film forming film 13 is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the protective film forming film 13 is not particularly limited, but is preferably 1 to 50 μm, and more preferably 3 to 40 μm. When the thickness of the protective film forming film 13 is at least the above lower limit value, the adhesive force of the protective film forming film 13 to the adherend (semiconductor wafer 8') becomes higher. Further, when the thickness of the protective film forming film 13 is not more than the upper limit value, the protective film forming film 13 can be cut more easily in the expanding step described later.
Here, the "thickness of the protective film forming film 13" means the thickness of the entire protective film forming film 13, and for example, the thickness of the protective film forming film 13 composed of a plurality of layers means the protective film. It means the total thickness of all the layers constituting the forming film 13.

The protective film forming film 13 can be formed by using a protective film forming composition described later, which contains the constituent material thereof.

In the laminated structure forming step, for example, a protective film forming composite sheet 1 in which the base material 11, the pressure-sensitive adhesive layer 12, and the protective film forming film 13 are laminated in this order in the thickness direction is used. The laminated structure 101 can be formed by attaching the protective film forming film 13 to the back surface 8b'of the semiconductor wafer 8'in which the modified layer 81'has been formed.
Further, for example, after the protective film forming film 13 is attached to the back surface 8b'of the semiconductor wafer 8'in which the modified layer 81'has been formed, the protective film forming film 13 is attached to the semiconductor wafer 8'. Even if the pressure-sensitive adhesive layer 12 of the support sheet 10 is attached to the surface (exposed surface, back surface) 13b opposite to the attachment surface (one surface) 13a to form the protective film forming composite sheet 1. , The laminated structure 101 can be formed.
In each of these methods, the modified layer 81'is formed inside the semiconductor wafer 8', and then the composite sheet 1 for forming a protective film is attached to the semiconductor wafer 8'.

On the other hand, in the laminated structure forming step, for example, a protective film forming composite sheet 1 is used, the protective film forming film 13 is attached to the back surface 8b'of the semiconductor wafer 8', and then the inside of the semiconductor wafer 8' By forming the modified layer 81'on the surface, the laminated structure 101 can be formed.
Further, for example, after the protective film forming film 13 is attached to the back surface 8b'of the semiconductor wafer 8', the adhesive layer 12 of the support sheet 10 is attached to the back surface 13b of the protective film forming film 13 to attach the protective film. The laminated structure 101 can also be formed by forming the modified layer 81'inside the semiconductor wafer 8'after forming the forming composite sheet 1.
All of these are methods in which the modified layer 81'is formed inside the semiconductor wafer 8'after the protective film forming composite sheet 1 is attached to the semiconductor wafer 8'.

Among these, in the manufacturing method 1, in the laminated structure forming step, the modified layer 81'is formed inside the semiconductor wafer 8', and then the protective film forming composite sheet 1 is attached to the semiconductor wafer 8'. It is preferable to keep the state in place. This is because, as will be described later, irradiation with laser light is required to form the modified layer 81'. By providing the semiconductor wafer 8'with the modified layer 81'formed in advance on the protective film forming film 13 and the support sheet 10 as described above, the support sheet 10 is formed in order to form the modified layer 81'. And, it is not necessary to irradiate the semiconductor wafer 8'with a laser beam by transmitting the protective film forming film 13. Therefore, the support sheet 10 and the protective film forming film 13 are not limited to those having the transmission of laser light, and those having no transmission of laser light can also be used, and the types of those to be used are limited. Absent.
Further, in order to enhance the transmission of laser light, the outermost surface (back surface) 10b (in other words, here, the base material) on the side opposite to the side on which the protective film forming film 13 of the support sheet 10 is provided is provided. Since it is not necessary to improve the smoothness of the exposed surface and the back surface 11b) of 11, it is possible to suppress the occurrence of blocking during storage of the support sheet 10.

The laminated structure 101 is preferably fixed to a ring frame or the like on the support sheet 10 as in the case of a conventional dicing sheet or the like, for example.

Of the semiconductor wafers 8'to which the protective film forming film 13 constituting the protective film forming composite sheet 1 or the protective film forming film 13 not forming the protective film forming composite sheet 1 is attached. It is preferable that a back grind tape is attached to the circuit forming surface 8a'. Even if the thickness of the semiconductor wafer 8'to which the back grind tape is attached is thin (even if the semiconductor wafer 8'is a thin wafer), until the protective film forming film 13 is attached. When handling the wafer, the occurrence of breakage such as cracks and chips is suppressed.
The back grind tape is used, for example, when grinding the back surface of the semiconductor wafer 8'as described later.

FIG. 2 is a cross-sectional view schematically showing the semiconductor wafer 8'to which the back grind tape is attached. A back grind tape 7 is attached to the circuit forming surface 8a'of the semiconductor wafer 8'shown here.

It is preferable that the back grind tape attached to the circuit forming surface 8a'of the semiconductor wafer 8'is removed (peeled) from the semiconductor wafer 8'after the laminated structure 101 is formed and before the expanding step described later is performed. .. After the laminated structure 101 is formed, the semiconductor wafer 8'is suppressed from being damaged both when the back grind tape is removed and after the back grind tape is removed.

○ Modified layer forming step In the semiconductor wafer 8', the modified layer 81'can be formed by, for example, irradiating a laser beam so as to focus on a focal point set inside the semiconductor wafer 8'.
That is, in the manufacturing method (1), the semiconductor wafer 8'before the protective film forming film 13 is provided is focused on the focus set inside the semiconductor wafer 8'before the laminated structure forming step. As described above, it is preferable to have a modified layer forming step of irradiating the semiconductor wafer 8'with a laser beam to form the modified layer 81'inside the semiconductor wafer 8'.

The laser light to be irradiated is preferably laser light in the infrared region.
When forming the modified layer 81', for example, in order to form the modified layer 81'while minimizing damage to the surface of the semiconductor wafer 8'and the region near the surface due to irradiation with laser light, the opening degree ( It is preferable to irradiate a laser beam having a large NA).

The thickness of the semiconductor wafer 8'(in other words, the semiconductor wafer 8'before the formation of the modified layer 81') to be formed of the modified layer 81'is not particularly limited as long as the effect of the present invention is not impaired. It is preferably 5 to 500 μm, more preferably 10 to 400 μm. When the thickness of the semiconductor wafer 8'is equal to or greater than the lower limit, the occurrence of breakage such as cracking or chipping of the semiconductor wafer 8'is further suppressed. Further, when the thickness of the semiconductor wafer 8'is equal to or less than the upper limit value, the semiconductor wafer 8'is more easily divided into the semiconductor chips 8 in the expanding step described later.

The thickness of the semiconductor wafer 8'can be adjusted by grinding the surface of the semiconductor wafer 8'on the side opposite to the circuit forming surface 8a' by a known method such as a method using a grinder. When the semiconductor wafer 8'is ground in this way, the back surface 8b'of the semiconductor wafer 8'to which the protective film forming film 13 is finally attached becomes a ground surface.

○ Expanding process (expanding process (E1))
In the expanding step (expanding step (E1)), the laminated structure 101 is expanded in the direction of the surface 13a of the protective film forming film 13 (the direction indicated by the arrow I in the drawing) and shown in FIG. 1B. As described above, the protective film forming film 13 is cut, and the semiconductor wafer 8'is divided at the site of the modified layer 81' to obtain a plurality of semiconductor chips 8.
Here, the protective film forming film 13 after cutting is indicated by reference numeral 131. In addition, in this specification, a film for forming a protective film after cutting may be simply referred to as "a film for forming a protective film".
Further, the "direction of the surface 13a of the protective film forming film 13" is synonymous with, for example, a direction parallel to one surface 11a of the base material 11 or one surface 12a of the pressure-sensitive adhesive layer 12.

By expanding, that is, expanding the laminated structure 101, the protective film forming film 13 is expanded together with the base material 11 and the pressure-sensitive adhesive layer 12 (in other words, the support sheet 10), and the protective film forming film 13 is cut. .. At the same time, by applying a force to the semiconductor wafer 8', the semiconductor wafer 8'is divided at the portion of the modified layer 81' to form a plurality of semiconductor chips 8. As a result, the protective film forming film 13 is cut at a target location along the outer shape of the semiconductor chip 8.

Since the protective film forming film 13 is energy ray-curable, it is not necessary to heat the protective film forming film 13 in order to form the protective film after this step. Therefore, as the support sheet 10 (for example, the base material 11), one having no heat resistance and a low elastic modulus can be used. As described above, by using the support sheet 10 having a low elastic modulus, the support sheet 10 can be easily expanded, and the protective film forming film 13 can be sufficiently cut at a target location.

In the expanding step, it is preferable to expand the laminated structure 101 while cooling the protective film forming film 13 to cut the protective film forming film 13. By doing so, the protective film forming film 13 can be easily cut.
The cooling temperature of the protective film forming film 13 at the time of expansion is not particularly limited, but is preferably −15 to 10 ° C. from the viewpoint that the protective film forming film 13 can be cut more easily.

The expanding speed (expansion speed) of the laminated structure 101 (protective film forming film 13) in the expanding step is not particularly limited as long as it does not impair the effects of the present invention, but is 0.5 to 100 mm / sec. It is preferably 1 to 60 mm / sec, and more preferably 1 to 60 mm / sec. When the expanding speed is in such a range, the effect of being able to cut the protective film forming film 13 efficiently and without accompanied by process abnormalities becomes higher. In particular, when the expanding speed is not more than the above upper limit value, the semiconductor chip 8 is less likely to be damaged, and the occurrence of abnormalities such as chipping at the cut portion of the protective film forming film 131 after cutting is further suppressed. ..

○ Protective film forming step (Protective film forming step (C1))
In the protective film forming step (protective film forming step (C1)), the protective film forming film 131 after cutting is irradiated with energy rays to form the protective film 131', as shown in FIG. 1 (c). As described above, a semiconductor chip 8 with a protective film (semiconductor chip 8 having a protective film 131'on the back surface 8b) is obtained. By this step, a plurality of target semiconductor chips 8 with protective films can be obtained at once. In FIG. 1C, the processed laminated structure in which a plurality of semiconductor chips 8 with protective films are provided on the support sheet 10 is indicated by reference numeral 101'. ..

In this step, heating is not required to form the protective film 131'as described above. Therefore, the decrease in the supportability (generation of slack) of the support sheet due to the influence of the contraction of the protective film 131'is suppressed.

When the protective film 131 is cured to form the protective film 131', the energy ray irradiation condition (curing condition) is such that the protective film 131'is sufficiently cured to exert its function. The limit is not particularly limited, and for example, it may be appropriately selected depending on the type of the protective film forming film 131.
For example, the illuminance of the energy rays at the time of curing the protective film forming film 131 is preferably ⁴ to 280 mW / cm ² . The amount of light of the energy rays at the time of curing is preferably ³ to 1000 mJ / cm ² .

In the manufacturing method (1), the laminated structure is not limited to the one shown here, and a part of the structure of the laminated structure 101 is changed, deleted or added within a range that does not impair the effect of the present invention. It may be.

For example, as a support sheet, in FIG. 1, an adhesive layer is provided on a base material, but the support sheet is a support sheet on which a layer other than the pressure-sensitive adhesive layer is provided. You may.
In the present invention, the support sheet is preferably provided with an adhesive layer on the base material, and more preferably provided with the pressure-sensitive adhesive layer in direct contact with the base material.

Further, up to this point, as one embodiment of the manufacturing method (1), the laminated structure forming step, the expanding step (E1), the protective film forming step (C1), and the modified layer forming step, if necessary, have been performed. Although the method for manufacturing a semiconductor chip with a protective film to have has been described, the manufacturing method (1) may have other steps other than these three steps or four steps as long as the effects of the present invention are not impaired. ..
The other steps can be arbitrarily selected depending on the intended purpose, and are not particularly limited.

When a laminated structure other than the laminated structure 101 is used in the manufacturing method (1), or when the manufacturing method (1) has the other steps, such a laminated structure is used in the above-described embodiment. By adding the step for forming and the other steps at appropriate timings, the method for manufacturing the semiconductor chip with a protective film according to the other embodiment in the manufacturing method (1) can be obtained.

◎ Manufacturing method of semiconductor chip with protective film (Manufacturing method (2))
In the method for manufacturing a semiconductor chip with a protective film of the present invention (manufacturing method (2)), an energy ray-curable protective film forming film is provided on a support sheet, and a semiconductor wafer is provided on the protective film forming film. A laminated structure forming step of forming a laminated structure in which a modified layer is formed inside the semiconductor wafer, and irradiating the protective film forming film with energy rays to form a protective film. The protective film forming step and the laminated structure after forming the protective film are expanded toward the surface of the protective film to cut the protective film and divide the semiconductor wafer at the site of the modified layer. It has an expanding step of obtaining a plurality of semiconductor chips with protective films.

In the manufacturing method (2) of the present invention, the order in which the step of forming the protective film and the step of expanding the laminated structure are performed is reversed from the case of the above-mentioned manufacturing method (1). ..
The production method (2) of the present invention has the same effect as the above-mentioned production method (1).

That is, according to the manufacturing method (2) of the present invention, since the protective film forming film is energy ray-curable, heating is not required to form the protective film, and the elastic modulus does not have heat resistance as a support sheet. Can be used with a low value. Therefore, the support sheet can be easily expanded and the protective film can be sufficiently cut. Further, since heating is not required to form the protective film, a decrease in supportability (generation of slack) on the support sheet of the semiconductor wafer is suppressed.

Further, according to the manufacturing method (2) of the present invention, in the laminated structure forming step, as will be described later, a semiconductor wafer on which a modified layer has been formed in advance is provided on the protective film forming film and the support sheet. It is possible. In this case, it is not necessary to irradiate the semiconductor wafer with laser light by transmitting the support sheet and the protective film forming film in order to form the modified layer, and the types of the support sheet and the protective film forming film that can be used are There is no limitation. Further, in order to increase the transmission of laser light, the smoothness of the outermost surface layer (for example, the exposed surface of the base material) on the side opposite to the side where the protective film forming film of the support sheet is provided is improved. Since it is not necessary to make the support sheet, it is possible to suppress the occurrence of blocking during storage of the support sheet.

Further, the manufacturing method (2) of the present invention avoids a problem by scraping a part of the semiconductor wafer such as blade dicing by adopting a method of dividing the semiconductor wafer at the site of the modified layer. It is advantageous in that it can be done.

Hereinafter, the manufacturing method (2) will be described in detail with reference to the drawings.
FIG. 3 is a cross-sectional view for schematically explaining an embodiment of the manufacturing method (2) of the present invention.

○ Laminated structure forming step In the laminated structure forming step of the manufacturing method (2), as shown in FIG. 3A, an energy ray-curable protective film forming film 13 is provided on the support sheet 10. The semiconductor wafer 8'is provided on the protective film forming film 13, and the laminated structure 101 in which the modified layer 81'is formed is formed inside the semiconductor wafer 8'.
The laminated structure forming step in the manufacturing method (2) is the same as the laminated structure forming step in the above-mentioned manufacturing method (1).

For example, in this step, it is preferable that the modified layer 81'is formed inside the semiconductor wafer 8'and then the protective film forming composite sheet 1 is attached to the semiconductor wafer 8'.
Further, the semiconductor wafer 8'to which the protective film forming film 13 constituting the protective film forming composite sheet 1 or the protective film forming film 13 not forming the protective film forming composite sheet 1 is attached. Of these, it is preferable that a back grind tape is attached to the circuit forming surface 8a'. In this case, it is preferable that the back grind tape is removed (peeled) from the semiconductor wafer 8'after the laminated structure 101 is formed and before the expanding step described later is performed.
Further, it is preferable that the laminated structure 101 is fixed to a ring frame or the like on the support sheet 10 as in the case of a conventional dicing sheet or the like.
Details of the laminated structure forming step in the manufacturing method (2) will be omitted.

○ Modified layer forming step In the semiconductor wafer 8', the modified layer 81'can be formed by, for example, irradiating a laser beam so as to focus on a focal point set inside the semiconductor wafer 8'.
That is, in the manufacturing method (2), the semiconductor wafer 8'before the protective film forming film 13 is provided is focused on the focus set inside the semiconductor wafer 8'before the laminated structure forming step. As described above, it is preferable to have a modified layer forming step of irradiating the semiconductor wafer 8'with a laser beam to form the modified layer 81'inside the semiconductor wafer 8'.
The modified layer forming step in the manufacturing method (2) is the same as the modified layer forming step in the manufacturing method (1) described above, and the details thereof will be omitted.

○ Protective film forming step (Protective film forming step (C2))
In the protective film forming step (protective film forming step (C2)), as shown in FIG. 3B, the protective film forming film 13 is irradiated with energy rays to form the protective film 132.
The protective film 132 is the same as the protective film 131 in the above-mentioned manufacturing method (1) except that it is not cut.
Further, in this step, the protective film forming step (1) in the above-mentioned manufacturing method (1) is performed, except that an uncut protective film forming film is used instead of the cut protective film forming film as the object to be cured. It can be performed by the same method as the protective film forming step (C1)). More specifically, it is as follows.

When the protective film 13 is cured to form the protective film 132, the energy ray irradiation condition (curing condition) is particularly high as long as the protective film 132 has a degree of curing sufficient to exert its function. It is not limited, and may be appropriately selected depending on, for example, the type of the protective film forming film 13.
For example, the illuminance of the energy rays at the time of curing the protective film forming film 13 is preferably ⁴ to 280 mW / cm ² . The amount of light of the energy rays at the time of curing is preferably ³ to 1000 mJ / cm ² .
In this step, heating is not required to form the protective film 132 in this way.

In the present invention, even after the protective film forming film is cured (the protective film is formed), the support sheet, the cured product of the protective film forming film (that is, the protective film), and the semiconductor wafer As long as the laminated structure is maintained, this laminated structure is referred to as a "laminated structure". In FIG. 3B, the laminated structure after the protective film forming film is cured (the protective film is formed) is indicated by reference numeral 102.

○ Expanding process (expanding process (E2))
In the expanding step (expanding step (E2)), the laminated structure 102 after forming the protective film 132 is expanded in the direction of the surface 132a of the protective film 132 (the direction indicated by the arrow I in the drawing), and FIG. As shown in c), the protective film 132 is cut, the semiconductor wafer 8'is divided at the site of the modified layer 81', and a plurality of semiconductor chips 8 with protective films (the back surface 8b is provided with the protective film 132'). Obtain a semiconductor chip 8). Here, the protective film 132 after cutting is indicated with reference numeral 132'. In addition, in this specification, a protective film after cutting may be simply referred to as a "protective film".

The “direction of the surface 132a of the protective film 132” is synonymous with, for example, a direction parallel to one surface 11a of the base material 11 or one surface 12a of the pressure-sensitive adhesive layer 12.
By this step, a plurality of target semiconductor chips 8 with protective films (semiconductor chips 8 having a protective film 132'on the back surface 8b) can be obtained at once. In FIG. 3C, the processed laminated structure in which a plurality of semiconductor chips 8 with protective films are provided on the support sheet 10 is indicated by reference numeral 102'. ..

In this step, the above-mentioned production method (1) is used except that, as the laminated structure which is the object of expansion, a film provided with a protective film which is a cured product thereof is used instead of the protective film forming film. It can be performed in the same manner as the expanding step (expanding step (E1)). More specifically, it is as follows.

By expanding, that is, expanding the laminated structure 102, the protective film 132 is expanded together with the base material 11 and the pressure-sensitive adhesive layer 12 (in other words, the support sheet 10), and the protective film 132 is cut. At the same time, by applying a force to the semiconductor wafer 8', the semiconductor wafer 8'is divided at the portion of the modified layer 81' to form a plurality of semiconductor chips 8. As a result, the protective film 132 is cut at a target location along the outer shape of the semiconductor chip 8.

Since the protective film forming film 13 is energy ray-curable, it is not necessary to heat the protective film forming film 13 in order to form the protective film before this step. Therefore, as the support sheet 10 (for example, the base material 11), one having no heat resistance and a low elastic modulus can be used. As described above, by using the support sheet 10 having a low elastic modulus, the support sheet 10 can be easily expanded and the protective film 132 can be sufficiently cut at a target location.

In the expanding step, the laminated structure 102 can be expanded while the protective film 132 is cooled to cut the protective film 132. By doing so, the protective film 132 can be easily cut.
The cooling temperature of the protective film 132 at the time of expansion is not particularly limited, but is preferably −15 to 10 ° C. from the viewpoint that the protective film 132 can be cut more easily.
In addition, unlike the case of the manufacturing method (1), the protective film 132 may be expanded at room temperature or while heating in some cases without cooling.

The expanding speed (expansion speed) of the laminated structure 102 (protective film 132) in the expanding step is not particularly limited as long as it does not impair the effects of the present invention, but is 0.5 to 100 mm / sec. Is preferable, and 1 to 60 mm / sec is more preferable. When the expanding speed is in such a range, the effect of being able to cut the protective film 132 efficiently and without accompanying a process abnormality becomes higher. In particular, when the expanding speed is not more than the upper limit value, the semiconductor chip 8 is less likely to be damaged, and the occurrence of abnormalities such as chipping of the protective film 132'after cutting is further suppressed.

The protective film 132'after cutting is substantially the same as the protective film 131'after cutting shown in FIG. 1 (c), and the laminated structure 102'after processing is processed as shown in FIG. 1 (c). It is substantially the same as the later laminated structure 101'.

Similar to the case of the manufacturing method (1), in the manufacturing method (2), the laminated structure is not limited to the one shown here, and the laminated structure 102 is one within a range not impairing the effect of the present invention. The structure of the part may be changed, deleted or added.

For example, as a support sheet, in FIG. 3, an adhesive layer is provided on a base material, but the support sheet is a support sheet on which a layer other than the pressure-sensitive adhesive layer is provided. You may.
In the present invention, the support sheet is preferably provided with an adhesive layer on the base material, and more preferably provided with the pressure-sensitive adhesive layer in direct contact with the base material.

Further, up to this point, as one embodiment of the manufacturing method (2), the laminated structure forming step, the protective film forming step (C2), the expanding step (E2), and, if necessary, the modified layer forming step have been performed. Although the method for manufacturing a semiconductor chip with a protective film having a protective film has been described, the manufacturing method (2) may have other steps other than these three steps or four steps as long as the effects of the present invention are not impaired. ..
The other steps can be arbitrarily selected depending on the intended purpose, and are not particularly limited.

When a laminated structure other than the laminated structure 102 is used in the manufacturing method (2), or when the manufacturing method (2) has the other steps, such a laminated structure is used in the above-described embodiment. By adding the step for forming and the other steps at appropriate timings, the method for manufacturing the semiconductor chip with a protective film according to the other embodiment in the manufacturing method (2) can be obtained.

As described above, in the manufacturing method (1) and the manufacturing method (2), the order of performing the step of forming the protective film and the step of expanding the laminated structure are reversed. Which manufacturing method is selected is arbitrary, and may be selected according to the purpose. Usually, the protective film forming film has a larger adhesive force to the adherend than the protective film, so the manufacturing method (1) for expanding the laminated structure provided with the protective film forming film is a semiconductor chip. It is highly effective in suppressing the scattering of the film (so-called chip flying).

Next, the composition and constituent materials of each component in the above-mentioned production method of the present invention will be described in detail.

◇ Base material The base material is in the form of a sheet or a film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); other than polyethylenes such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyethylene; ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as monomer) (Copolymers obtained using); Vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained using vinyl chloride as the monomer); Polystyrene; Polycycloolefins; Polyethylene terephthalate, polyethylene Polymers such as naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalenedicarboxylate, all aromatic polyesters in which all constituent units have aromatic cyclic groups; co-polymers of two or more of the above polymers. Polymers; poly (meth) acrylic acid esters; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene oxides; polyphenylene sulfides; polysulfones; polyether ketones and the like.
Further, examples of the resin include polymer alloys such as a mixture of the polyester and other resins. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.
Further, as the resin, for example, a crosslinked resin obtained by cross-linking one or more of the resins exemplified above; modification of an ionomer or the like using one or more of the resins exemplified so far. Resin is also mentioned.

In addition, in this specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth) acrylic acid.

The resin constituting the base material may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

It is preferable that the base material has a high accuracy of thickness, that is, a base material in which variation in thickness is suppressed regardless of the site. Among the above-mentioned constituent materials, as a material that can be used to construct a base material having such a high accuracy of thickness, for example, polyethylene, polyolefin other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer and the like are used. Can be mentioned.

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

◇ Adhesive layer The adhesive layer is in the form of a sheet or a film and contains an adhesive.
Examples of the pressure-sensitive adhesive include adhesive resins such as acrylic resin, urethane-based resin, rubber-based resin, silicone-based resin, epoxy-based resin, polyvinyl ether, polycarbonate, and ester-based resin, and acrylic-based resin is preferable. ..

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

The pressure-sensitive adhesive layer may be formed by using an energy ray-curable pressure-sensitive adhesive or may be formed by using a non-energy ray-curable pressure-sensitive adhesive.

<< Adhesive composition >>
The pressure-sensitive adhesive layer can be formed by using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive layer can be formed on a target portion by applying the pressure-sensitive adhesive composition to the surface to be formed of the pressure-sensitive adhesive layer and drying it if necessary. A more specific method for forming the pressure-sensitive adhesive layer will be described in detail later together with a method for forming the other layers. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer. In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The pressure-sensitive adhesive composition may be applied by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and a screen coater. , A method using various coaters such as a Meyer bar coater and a kiss coater.

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

When the pressure-sensitive adhesive layer is energy ray-curable, the pressure-sensitive adhesive composition containing the energy ray-curable pressure-sensitive adhesive, that is, the energy ray-curable pressure-sensitive adhesive composition, for example, is a non-energy ray-curable pressure-sensitive adhesive. Adhesive composition (I-1) containing a resin (I-1a) (hereinafter, may be abbreviated as "adhesive resin (I-1a)") and an energy ray-curable compound; non-energy An energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the linear curable adhesive resin (I-1a) (hereinafter referred to as "adhesive resin (I-2a)"). A pressure-sensitive adhesive composition (I-2) containing (may be abbreviated); a pressure-sensitive adhesive composition (I-3) containing the pressure-sensitive resin (I-2a) and an energy ray-curable compound, etc. Can be mentioned.

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

[Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin include acrylic polymers having at least a structural unit derived from (meth) acrylic acid alkyl ester.
The structural unit of the acrylic resin may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

Examples of the (meth) acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is linear or branched. Is preferable.
More specifically, as the (meth) acrylic acid alkyl ester, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, (meth) acrylic acid. n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) 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, (meth) ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl acrylate (meth), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, ( Hexadecyl acrylate ((meth) palmityl acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecil (meth) acrylate, icosyl (meth) acrylate, etc. Can be mentioned.

From the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer, the acrylic polymer preferably has a structural unit derived from a (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group. The alkyl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms, from the viewpoint of further improving the adhesive strength of the pressure-sensitive adhesive layer. Further, the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group is preferably an acrylic acid alkyl ester.

The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester.
As the functional group-containing monomer, for example, the functional group may be a starting point of cross-linking by reacting with a cross-linking agent described later, or the functional group may react with an unsaturated group in an unsaturated group-containing compound described later. Then, there is one that enables the introduction of an unsaturated group into the side chain of the acrylic polymer.

Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). (Meta) hydroxyalkyl acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylics such as vinyl alcohol and allyl alcohol. Saturated alcohol (unsaturated alcohol having no (meth) acrylic skeleton) and the like can be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, and citracon. Ethylene unsaturated dicarboxylic acids such as acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like. Be done.

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

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

In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 32% by mass, based on the total amount of the structural units. It is particularly preferably 3 to 30% by mass.

The acrylic polymer may further have a structural unit derived from another monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester and the structural unit derived from the functional group-containing monomer.
The other monomer is not particularly limited as long as it can be copolymerized with a (meth) acrylic acid alkyl ester or the like.
Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide and the like.

The other monomer constituting the acrylic polymer may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

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

The pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total content of the components other than the solvent (that is, of the pressure-sensitive adhesive resin (I-1a) of the pressure-sensitive adhesive layer). The content) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Among the energy ray-curable compounds, examples of the monomer include trimethylpropantri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4. Polyvalent (meth) acrylates such as −butylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( Meta) acrylate and the like can be mentioned.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer obtained by polymerizing the monomers exemplified above.
The energy ray-curable compound has a relatively large molecular weight, and urethane (meth) acrylate and urethane (meth) acrylate oligomer are preferable in that the storage elastic modulus of the pressure-sensitive adhesive layer is not easily lowered.

The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

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

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from the (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), the pressure-sensitive adhesive composition ( I-1) preferably further contains a cross-linking agent.

The cross-linking agent, for example, reacts with the functional group to cross-link the adhesive resins (I-1a) with each other.
Examples of the cross-linking agent include isocyanate-based cross-linking agents such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates (cross-linking agents having an isocyanate group); and epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (cross-linking agents). Crosslinking agent having a glycidyl group); Isocyanate-based crosslinking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (crosslinking agent having an aziridinyl group); Metal chelate-based crosslinking agent such as aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent having an isocyanurate skeleton) and the like.
The cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoints of improving the cohesive force of the pressure-sensitive adhesive and lowering the adhesive force of the pressure-sensitive adhesive layer and being easily available.

The cross-linking agent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[Photopolymerization initiator]
The pressure-sensitive adhesive composition (I-1) may further contain a photopolymerization initiator. The pressure-sensitive adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy. -2-Methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hirodoxy-1- {4- [4- (2-hydroxy-2) -Acetphenone compounds such as -methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Acylphosphine oxide compounds such as oxides; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketor compounds such as 1-hydroxycyclohexylphenylketone; azo compounds such as azobisisobutyronitrile; Titanocene compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4 -(1-Methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
Further, as the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound, and is 0. It is more preferably .03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-1) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust preventives, colorants (pigments, dyes), sensitizers, and tackifiers. , Known additives such as reaction retarders and cross-linking accelerators (catalysts).
The reaction retarder means that, for example, due to the action of the catalyst mixed in the pressure-sensitive adhesive composition (I-1), an unintended cross-linking reaction occurs in the pressure-sensitive adhesive composition (I-1) during storage. It suppresses the progress. Examples of the reaction retarder include those that form a chelate complex by chelating to a catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule. Can be mentioned.

The other additives contained in the pressure-sensitive adhesive composition (I-1) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

The content of the other additives in the pressure-sensitive adhesive composition (I-1) is not particularly limited, and may be appropriately selected depending on the type thereof.

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

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

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

The solvent contained in the pressure-sensitive adhesive composition (I-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

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

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

In addition to the energy ray-polymerizable unsaturated group, the unsaturated group-containing compound can further bond with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). It is a compound having a group.
Examples of the energy ray-polymerizable unsaturated group include (meth) acryloyl group, vinyl group (ethenyl group), allyl group (2-propenyl group) and the like, and (meth) acryloyl group is preferable.
Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amino group, and a hydroxyl group and an amino group that can be bonded to a carboxy group or an epoxy group. And so on.

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

The pressure-sensitive adhesive resin (I-2a) contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the pressure-sensitive adhesive composition (I-2), the ratio of the content of the pressure-sensitive adhesive resin (I-2a) to the total content of the components other than the solvent (that is, of the pressure-sensitive adhesive resin (I-2a) of the pressure-sensitive adhesive layer). The content) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 10 to 90% by mass.

[Crosslinking agent]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer similar to that in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), for example, the pressure-sensitive adhesive composition ( I-2) may further contain a cross-linking agent.

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-2) include the same cross-linking agents as those in the pressure-sensitive adhesive composition (I-1).
The cross-linking agent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, two or more types, and when two or more types, the combination and ratio thereof can be arbitrarily selected.

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

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

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-2) include the same photopolymerization initiators in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-2) may be only one type, two or more types, and when two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive in the pressure-sensitive adhesive composition (I-2) include the same as the other additives in the pressure-sensitive adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-2) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-2) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
In the pressure-sensitive adhesive composition (I-2), the content of the solvent is not particularly limited and may be appropriately adjusted.

<Adhesive composition (I-3)>
As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive resin (I-2a) and an energy ray-curable compound.

In the pressure-sensitive adhesive composition (I-3), the ratio of the content of the pressure-sensitive adhesive resin (I-2a) to the total content of the components other than the solvent (that is, of the pressure-sensitive adhesive resin (I-2a) of the pressure-sensitive adhesive layer). The content) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.

[Energy ray curable compound]
Examples of the energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays, and the pressure-sensitive adhesive composition. Examples thereof include the same energy ray-curable compounds contained in the substance (I-1).
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected. ..

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

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

Examples of the photopolymerization initiator in the pressure-sensitive adhesive composition (I-3) include the same photopolymerization initiators in the pressure-sensitive adhesive composition (I-1).
The photopolymerization initiator contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

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

[Other additives]
The pressure-sensitive adhesive composition (I-3) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive include the same as the other additive in the pressure-sensitive adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, their combinations and ratios can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-3) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-3) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.
In the pressure-sensitive adhesive composition (I-3), the content of the solvent is not particularly limited and may be appropriately adjusted.

<Adhesive compositions other than adhesive compositions (I-1) to (I-3)>
Up to this point, the pressure-sensitive adhesive composition (I-1), the pressure-sensitive adhesive composition (I-2), and the pressure-sensitive adhesive composition (I-3) have been mainly described, but those described as the components contained therein have been described. General pressure-sensitive adhesive compositions other than these three types of pressure-sensitive adhesive compositions (referred to in this specification as "pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)") However, it can be used in the same way.

Examples of the pressure-sensitive adhesive composition other than the pressure-sensitive adhesive compositions (I-1) to (I-3) include non-energy ray-curable pressure-sensitive adhesive compositions in addition to the energy-ray-curable pressure-sensitive adhesive composition.
Examples of the non-energy ray-curable pressure-sensitive adhesive composition include non-energy ray-curable resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. Examples thereof include a pressure-sensitive adhesive composition (I-4) containing a sex-sensitive pressure-sensitive resin (I-1a), and those containing an acrylic resin are preferable.

The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) preferably contain one or more cross-linking agents, and the content thereof is the above-mentioned pressure-sensitive adhesive composition. The same can be applied to the case of (I-1) and the like.

<Adhesive composition (I-4)>
Preferred pressure-sensitive adhesive compositions (I-4) include, for example, those containing the pressure-sensitive adhesive resin (I-1a) and a cross-linking agent.

[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-4) include the same adhesive resin (I-1a) as in the pressure-sensitive adhesive composition (I-1).
The pressure-sensitive adhesive resin (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. You can choose.

In the pressure-sensitive adhesive composition (I-4), the ratio of the content of the pressure-sensitive adhesive resin (I-1a) to the total content of the components other than the solvent (that is, of the pressure-sensitive adhesive resin (I-1a) of the pressure-sensitive adhesive layer). The content) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass.

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

Examples of the cross-linking agent in the pressure-sensitive adhesive composition (I-4) include the same cross-linking agents as those in the pressure-sensitive adhesive composition (I-1).
The cross-linking agent contained in the pressure-sensitive adhesive composition (I-4) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

In the pressure-sensitive adhesive composition (I-4), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the content of the pressure-sensitive adhesive resin (I-1a). It is more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass.

[Other additives]
The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-mentioned components as long as the effects of the present invention are not impaired.
Examples of the other additive include the same as the other additive in the pressure-sensitive adhesive composition (I-1).
The other additives contained in the pressure-sensitive adhesive composition (I-4) may be only one kind, two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

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

[solvent]
The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the pressure-sensitive adhesive composition (I-1).
Examples of the solvent in the pressure-sensitive adhesive composition (I-4) include the same solvents as those in the pressure-sensitive adhesive composition (I-1).
The solvent contained in the pressure-sensitive adhesive composition (I-4) may be only one kind, two or more kinds, and when two or more kinds, the combination and ratio thereof can be arbitrarily selected.
In the pressure-sensitive adhesive composition (I-4), the content of the solvent is not particularly limited and may be appropriately adjusted.

<< Manufacturing method of adhesive composition >>
The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive composition (I-4) , The pressure-sensitive adhesive and, if necessary, components other than the pressure-sensitive adhesive, and the like, are obtained by blending each component for forming a pressure-sensitive adhesive composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

◇ Protective film forming film The protective film forming film is cured by irradiation with energy rays to become a protective film. This protective film is for protecting the back surface of the semiconductor wafer or semiconductor chip (the surface opposite to the circuit forming surface). The protective film forming film is soft and can be easily attached to the object to be attached.
Since the protective film forming film is energy ray-curable, the protective film can be formed by curing in a shorter time than the thermosetting protective film forming film.
By providing the protective film forming film on the support sheet, the protective film forming composite sheet can be formed.

In the present specification, the "protective film forming film" means a film before curing, and the "protective film" means a cured film for forming a protective film.

Examples of the protective film forming film include those containing an energy ray-curable component (a) described later.
The energy ray-curable component (a) is preferably uncured, preferably sticky, and more preferably uncured and sticky.

The protective film-forming film can be produced by applying a protective film-forming composition, which will be described later, to the surface to be formed of the protective film-forming film and, if necessary, drying it.

For example, when the protective film-forming film is provided with release films on both sides thereof, the coated surface of the protective film-forming composition is the surface of either one of these release films (preferably the release-treated surface). Can be. On the other hand, when the protective film-forming film is provided on the support sheet, the coated surface of the protective film-forming composition can be the surface of the support sheet.

<< Composition for forming a protective film >>
The protective film-forming film can be formed by using a protective film-forming composition containing the constituent material. For example, a protective film-forming film can be formed at a target site by applying the protective film-forming composition to the surface to be formed of the protective film-forming film and drying it if necessary. The ratio of the contents of the components that do not vaporize at room temperature in the protective film-forming composition is usually the same as the ratio of the contents of the components in the protective film-forming film.

The composition for forming a protective film may be applied by a known method, for example, an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, and the like. A method using various coaters such as a screen coater, a Meyer bar coater, and a knife coater can be mentioned.

The drying conditions of the protective film-forming composition are not particularly limited, but when the protective film-forming composition contains a solvent described later, it is preferably heat-dried. In this case, for example, 70 to 130 ° C. It is preferable to dry under the condition of 10 seconds to 5 minutes.

<Composition for forming a protective film (IV-1)>
Examples of the protective film-forming composition include the protective film-forming composition (IV-1) containing the energy ray-curable component (a).

[Energy ray curable component (a)]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film-forming property, flexibility, and the like to the protective film-forming film.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000, and an energy ray-curable group having a molecular weight of 100 to 80,000. The compound (a2) can be mentioned. At least a part of the polymer (a1) may be crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.
In the present specification, the weight average molecular weight means a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

(Polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000)
Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2000000 include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, and the above. Examples thereof include an acrylic resin (a1-1) obtained by polymerizing a group that reacts with a functional group and an energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond. ..

Examples of the functional group capable of reacting with a group of another compound include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than the hydrogen atom. Group), epoxy group and the like. However, from the viewpoint of preventing corrosion of circuits such as semiconductor wafers and semiconductor chips, the functional group is preferably a group other than a carboxy group.
Among these, the functional group is preferably a hydroxyl group.

-Acrylic polymer having a functional group (a11)
Examples of the acrylic polymer (a11) having the functional group include those obtained by copolymerizing the acrylic monomer having the functional group and the acrylic monomer having no functional group. In addition to the monomer, a monomer other than the acrylic monomer (non-acrylic monomer) may be copolymerized.
Further, the acrylic polymer (a11) may be a random copolymer or a block copolymer.

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

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). (Meta) hydroxyalkyl acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylics such as vinyl alcohol and allyl alcohol. Saturated alcohol (unsaturated alcohol having no (meth) acrylic skeleton) and the like can be mentioned.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, and citracon. Ethylene unsaturated dicarboxylic acids such as acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the ethylenically unsaturated dicarboxylic acids; (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate and the like. Be done.

The acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer or a carboxy group-containing monomer, and more preferably a hydroxyl group-containing monomer.

The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof are arbitrary. You can choose.

Examples of the acrylic monomer having no functional group include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n (meth) acrylic acid. -Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ( 2-Ethylhexyl acrylate, (meth) isooctyl acrylate, n-octyl acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) Undecyl acrylate, dodecyl (meth) acrylate (lauryl acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl acrylate), pentadecyl (meth) acrylate, (meth) ) Hexadecyl acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate) and other alkyl groups constituting the alkyl ester have 1 carbon number. Examples thereof include (meth) acrylic acid alkyl esters having a chain structure of ~ 18.

Examples of the acrylic monomer having no functional group include alkoxy such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Alkyl group-containing (meth) acrylic acid ester; (meth) acrylic acid ester having an aromatic group, including (meth) acrylic acid aryl ester such as (meth) phenyl acrylate; non-crosslinkable (meth) acrylamide and Derivatives thereof; (meth) acrylic acid ester having a non-crosslinkable tertiary amino group such as (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl and the like can also be mentioned. ..

The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

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

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

The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof may be arbitrary. You can choose.

In the protective film forming composition (IV-1), the content of the acrylic resin (a1-1) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and 3 It is particularly preferably ~ 20% by mass.

-Energy ray curable compound (a12)
The energy ray-curable compound (a12) is one or two selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group as a group capable of reacting with the functional group of the acrylic polymer (a11). Those having the above are preferable, and those having an isocyanate group as the group are more preferable. When the energy ray-curable compound (a12) has an isocyanate group as the group, for example, 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 in one molecule, and more preferably 1 to 3 groups.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloyloxymethyl). Ethyl isocyanate;
Acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate;
Examples thereof include an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and a hydroxyethyl (meth) acrylate.
Among these, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

In the acrylic resin (a1-1), the content of the energy ray-curable group derived from the energy ray-curable compound (a12) is relative to the content of the functional group derived from the acrylic polymer (a11). Is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the ratio of the content is in such a range, the adhesive force of the protective film formed by curing becomes larger. When the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the content ratio is 100 mol%. When the energy ray-curable compound (a12) is a polyfunctional compound (having two or more of the groups in one molecule), the upper limit of the content ratio may exceed 100 mol%.

The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 20,000, more preferably 300,000 to 1,500,000.

When the polymer (a1) is at least partially crosslinked with a cross-linking agent (f), the polymer (a1) has been described as constituting the acrylic polymer (a11). , A monomer that does not correspond to any of the above-mentioned monomers and has a group that reacts with the cross-linking agent (f) may be polymerized and cross-linked at the group that reacts with the cross-linking agent (f). However, the group that reacts with the functional group derived from the energy ray-curable compound (a12) may be crosslinked.

The protective film-forming composition (IV-1) and the polymer (a1) contained in the protective film-forming film may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

(Compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000)
Examples of the energy ray-curable group contained in the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000 include a group containing an energy ray-curable double bond, and preferred one is (meth). Examples include an acryloyl group and a vinyl group.

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

Among the compounds (a2), examples of the low molecular weight compound having an energy ray-curable group include polyfunctional monomers or oligomers, and acrylate compounds having a (meth) acryloyl group are preferable.
Examples of the acrylate-based compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4. -((Meta) acryloxipolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxidiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloyloxypolypropoxy) phenyl] propane, tricyclodecanedimethanol di (meth) acrylate (tri) Cyclodecanedimethylol di (meth) acrylate), 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene Glycoldi (meth) acrylate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy- Bifunctional (meth) acrylates such as 1,3-di (meth) acryloxypropane;
Tris (2- (meth) acryloxyethyl) isocyanurate, ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa ( Polyfunctional (meth) acrylates such as meta) acrylates;
Examples thereof include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

Among the compounds (a2), an epoxy resin having an energy ray-curable group and a phenol resin having an energy ray-curable group are described, for example, in paragraph 0043 of "Japanese Patent Laid-Open No. 2013-194102". Can be used. Such a resin also corresponds to a resin constituting the thermosetting component (h) described later, but is treated as the compound (a2) in the present invention.

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

The protective film-forming composition (IV-1) and the compound (a2) contained in the protective film-forming film may be only one kind, two or more kinds, or a combination thereof when there are two or more kinds. And the ratio can be selected arbitrarily.

[Polymer without energy ray-curable group (b)]
When the protective film-forming composition (IV-1) and the protective film-forming film contain the compound (a2) as the energy ray-curable component (a), the polymer does not further have an energy ray-curable group. (B) is also preferably contained.
The polymer (b) may be at least partially crosslinked by a crosslinking agent (f) or may not be crosslinked.

Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, and polyester urethanes. Examples include resin.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter, may be abbreviated as "acrylic polymer (b-1)").

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

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

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n- (meth) acrylic acid. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) ) 2-Ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) n-octyl acrylate, (meth) n-nonyl acrylate, (meth) isononyl acrylate, (meth) decyl acrylate, (meth) acrylic Undecyl acrylate, dodecyl (meth) acrylate (lauryl acrylate (meth), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl acrylate), pentadecyl (meth) acrylate, (meth) Alkyl groups constituting alkyl esters such as hexadecyl acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate) have 1 to 1 carbon atoms. Examples thereof include (meth) acrylic acid alkyl ester having a chain structure of 18.

Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid isobornyl and (meth) acrylic acid dicyclopentanyl;
(Meta) Acrylic acid aralkyl esters such as benzyl (meth) acrylic acid;
(Meta) Acrylic acid cycloalkenyl ester such as (meth) acrylic acid dicyclopentenyl ester;
Examples thereof include (meth) acrylic acid cycloalkenyloxyalkyl esters such as (meth) acrylic acid dicyclopentenyloxyethyl ester.

Examples of the glycidyl group-containing (meth) acrylic acid ester include glycidyl (meth) acrylic acid.
Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxy (meth) acrylate. Examples thereof include propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the substituted amino group-containing (meth) acrylic acid ester include N-methylaminoethyl (meth) acrylic acid.

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

As the polymer (b) having no energy ray-curable group, which is at least partially crosslinked by the cross-linking agent (f), for example, the reactive functional group in the polymer (b) is the cross-linking agent (f). ) And those that reacted.
The reactive functional group may be appropriately selected depending on the type of the cross-linking agent (f) and the like, and is not particularly limited. For example, when the cross-linking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, an amino group and the like, and among these, a hydroxyl group having a high reactivity with an isocyanate group. Is preferable. When the cross-linking agent (f) is an epoxy-based compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group and the like, and among these, carboxy having a high reactivity with an epoxy group. Groups are preferred. However, from the viewpoint of preventing corrosion of circuits of semiconductor wafers and semiconductor chips, the reactive functional group is preferably a group other than a carboxy group.

Examples of the polymer (b) having the reactive functional group and not having the energy ray-curable group include those obtained by polymerizing at least the monomer having the reactive functional group. In the case of the acrylic polymer (b-1), one or both of the acrylic monomer and the non-acrylic monomer listed as the monomers constituting the acrylic polymer (b-1) having the reactive functional group. It may be used. For example, examples of the polymer (b) having a hydroxyl group as a reactive functional group include those obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester, and other examples thereof have been mentioned above. Examples of the acrylic monomer or non-acrylic monomer obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted with the reactive functional group can be mentioned.

In the polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having the reactive functional group to the total amount of the structural units constituting the polymer (b) is 1 to 25. It is preferably by mass, more preferably 2 to 20% by mass. When the ratio is in such a range, the degree of cross-linking in the polymer (b) becomes a more preferable range.

The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is 1000 to 2000000 from the viewpoint of improving the film-forming property of the protective film-forming composition (IV-1). It is preferable, and it is more preferable that it is 100,000 to 1500,000.

The polymer (b) having no energy ray-curable group contained in the protective film forming composition (IV-1) and the protective film forming film may be only one kind or two or more kinds. In the case of species or more, their combinations and ratios can be arbitrarily selected.

Examples of the protective film-forming composition (IV-1) include those containing either or both of the polymer (a1) and the compound (a2). When the protective film forming composition (IV-1) contains the compound (a2), it preferably also contains a polymer (b) having no energy ray-curable group, and in this case, further. It is also preferable to contain the above (a1). Further, the protective film forming composition (IV-1) does not contain the compound (a2), but contains both the polymer (a1) and the polymer (b) having no energy ray-curable group. You may be.

When the protective film-forming composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the protective film-forming composition. In (IV-1), the content of the compound (a2) is 10 to 10 parts by mass with respect to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. It is preferably 400 parts by mass, more preferably 30 to 350 parts by mass.

In the protective film forming composition (IV-1), the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group with respect to the total content of the components other than the solvent. (That is, the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group) of the protective film-forming film may be 5 to 90% by mass. It is preferably 10 to 80% by mass, more preferably 15 to 70% by mass. When the ratio of the total content is in such a range, the energy ray curability of the protective film forming film becomes better.

When the protective film-forming composition (IV-1) contains the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the protective film-forming composition (IV-1) is contained. ) And the film for forming a protective film, the content of the polymer (b) is preferably 3 to 160 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable component (a). More preferably, it is ~ 130 parts by mass. When the content of the polymer (b) is in such a range, the energy ray curability of the protective film forming film becomes better.

In addition to the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the protective film-forming composition (IV-1) is a photopolymerization initiator (c) depending on the purpose. , Filler (d), coupling agent (e), cross-linking agent (f), colorant (g), thermosetting component (h), curing accelerator (i), and general-purpose additive (z). It may contain one or more selected from the group.
For example, the protective film-forming film formed by using the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h) is heated. The adhesive force to the adherend is improved, and the strength of the protective film formed from the protective film forming film is also improved.

[Photopolymerization Initiator (c)]
Examples of the photopolymerization initiator (c) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; acetophenone, 2 Acetphenone compounds such as −hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenylketone Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanosen; thioxanthone compounds such as thioxanthone; benzophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, Benzoyl compounds such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime); peroxide compounds; diketone compounds such as diacetyl Benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone; 2-chloroanthraquinone and the like.
Further, as the photopolymerization initiator (c), for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

The photopolymerization initiator (c) contained in the protective film forming composition (IV-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof are arbitrary. Can be selected.

When the photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the protective film forming composition (IV-1) is 100 parts by mass of the content of the energy ray-curable compound (a). On the other hand, the amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass.

[Filler (d)]
Since the protective film-forming film contains the filler (d), the protective film obtained by curing the protective film-forming film has an easy adjustment of the coefficient of thermal expansion, and the coefficient of thermal expansion of the protective film By optimizing for the object to be formed, the reliability of the package obtained by using this protective film is further improved. Further, when the protective film forming film contains the filler (d), the hygroscopicity of the protective film can be reduced and the heat dissipation can be improved.
Examples of the filler (d) include those made of a heat conductive material.

The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride and the like; spherical beads of these inorganic fillers; surface modification of these inorganic fillers. Goods; Single crystal fibers of these inorganic fillers; Glass fibers and the like.
Among these, the inorganic filler is preferably silica or alumina.

The average particle size of the filler (d) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 15 μm, and particularly preferably 0.3 to 10 μm. .. When the average particle size of the filler (d) is in such a range, it is possible to suppress a decrease in the light transmittance of the protective film while maintaining the adhesiveness to the object to be formed of the protective film.
In the present specification, the "average particle size" means the value of the particle size (D ₅₀ ) at an integrated value of 50% in the particle size distribution curve obtained by the laser diffraction / scattering method unless otherwise specified. ..

The protective film-forming composition (IV-1) and the filler (d) contained in the protective film-forming film may be only one type, two or more types, or a combination thereof when two or more types are used. And the ratio can be selected arbitrarily.

When the filler (d) is used, the ratio of the content of the filler (d) to the total content of all the components other than the solvent in the protective film forming composition (IV-1) (that is, for forming the protective film). The content of the filler (d) in the film) is preferably 5 to 83% by mass, more preferably 7 to 78% by mass. When the content of the filler (d) is in such a range, the above-mentioned coefficient of thermal expansion can be easily adjusted.

[Coupling agent (e)]
By using a coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness and adhesion of the protective film forming film to the adherend can be improved. Further, by using the coupling agent (e), the protective film obtained by curing the protective film-forming film has improved water resistance without impairing heat resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the energy ray-curable component (a), the polymer (b) having no energy ray-curable group, or the like. More preferably, it is a silane coupling agent.
Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-. (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-amino) Ethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.

The protective film forming composition (IV-1) and the coupling agent (e) contained in the protective film forming film may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

When the coupling agent (e) is used, the content of the coupling agent (e) in the protective film forming composition (IV-1) and the protective film forming film is the energy ray-curable component (a) and the energy. The total content of the polymer (b) having no linear curable group is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass. It is particularly preferably 0.1 to 5 parts by mass. When the content of the coupling agent (e) is at least the lower limit value, the dispersibility of the filler (d) in the resin is improved and the adhesiveness of the protective film forming film to the adherend is improved. The effect of using the coupling agent (e) is more remarkable. Further, when the content of the coupling agent (e) is equal to or less than the upper limit value, the generation of outgas is further suppressed.

[Crosslinking agent (f)]
By cross-linking the above-mentioned energy ray-curable component (a) or polymer (b) having no energy ray-curable group with a cross-linking agent (f), the initial adhesive force and cohesive force of the protective film forming film Can be adjusted.

Examples of the cross-linking agent (f) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (cross-linking agent having an aziridinyl group), and the like. Can be mentioned.

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively referred to as “aromatic polyvalent isocyanate compound and the like”. (May be abbreviated); trimerics such as the aromatic polyvalent isocyanate compound, isocyanurates and adducts; terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the like with a polyol compound. And so on. The "adduct" is a low content of the aromatic polyhydric isocyanate compound, the aliphatic polyvalent isocyanate compound or the alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil and the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include a xylylene diisocyanate adduct of trimethylol propane as described later. Further, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.

More specifically, as the organic polyvalent isocyanate compound, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4. , 4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Compounds in which one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or some hydroxyl groups of a polyol such as propane; lysine diisocyanate and the like can be mentioned.

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylpropan-tri-β-aziridinyl propionate, and tetramethylolmethane. Examples thereof include -tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.

When an organic polyvalent isocyanate compound is used as the cross-linking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group. When the cross-linking agent (f) has an isocyanate group and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the cross-linking agent (f) and the energy ray-curable The crosslinked structure can be easily introduced into the protective film-forming film by the reaction with the component (a) or the polymer (b) having no energy ray-curable group.

The cross-linking agent (f) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, or a combination thereof when two or more types are used. And the ratio can be selected arbitrarily.

When the cross-linking agent (f) is used, in the protective film-forming composition (IV-1), the content of the cross-linking agent (f) is a weight having no energy ray-curable component (a) and an energy ray-curable group. The total content of the coalescence (b) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass. It is particularly preferable to have. When the content of the cross-linking agent (f) is at least the lower limit value, the effect of using the cross-linking agent (f) is more remarkable. Further, when the content of the cross-linking agent (f) is not more than the upper limit value, the excessive use of the cross-linking agent (f) is suppressed.

[Colorant (g)]
Examples of the colorant (g) include known ones such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigments and organic dyes include aminium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squalium pigments, azulenium pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, and phthalocyanines. Colors, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments , Pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt dyes), dithiol metal complex pigments, indolphenol pigments, triallylmethane pigments, anthraquinone pigments, dioxazine pigments, naphthol pigments, azomethine pigments. Examples thereof include dyes, benzimidazolone dyes, pyranthron dyes and slene colors.

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

The colorant (g) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one kind, two or more kinds, and when two or more kinds, a combination thereof. And the ratio can be selected arbitrarily.

When the colorant (g) is used, the content of the colorant (g) in the protective film forming film may be appropriately adjusted according to the intended purpose. For example, when the print visibility is adjusted by adjusting the content of the colorant (g) and the light transmittance of the protective film, in the protective film forming composition (IV-1), other than the solvent. The ratio of the content of the colorant (g) to the total content of all the components (that is, the content of the colorant (g) of the protective film forming film) is preferably 0.1 to 10% by mass. , 0.4 to 7.5% by mass is more preferable, and 0.8 to 5% by mass is particularly preferable. When the content of the colorant (g) is at least the lower limit, the effect of using the colorant (g) is more remarkable. Further, when the content of the colorant (g) is not more than the upper limit value, the excessive use of the colorant (g) is suppressed.

[Thermosetting component (h)]
The thermosetting component (h) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one kind, two or more kinds, and when two or more kinds, they are used. The combination and ratio of are arbitrarily selectable.

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

(Epoxy thermosetting resin)
The epoxy-based thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2).
The epoxy-based thermosetting resin contained in the protective film forming composition (IV-1) and the protective film forming film may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.

-Epoxy resin (h1)
Examples of the epoxy resin (h1) include known ones, such as polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, and dicyclopentadiene type epoxy resin. Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other bifunctional or higher functional epoxy compounds can be mentioned.

As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group may be used. An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the protective film is improved.

Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of the epoxy group of the polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth) acrylic acid or a derivative thereof.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth) acryloyl group, and a (meth) group. Examples thereof include an acrylamide group, and an acryloyl group is preferable.

The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30,000, preferably 400 to 10000, from the viewpoint of curability of the protective film forming film and the strength and heat resistance of the protective film. It is more preferable that there is, and it is particularly preferable that it is 500 to 3000.
The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, more preferably 150 to 800 g / eq.

As the epoxy resin (h1), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

・ Thermosetting agent (h2)
The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).
Examples of the thermosetting agent (h2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is anhydrous, and the phenolic hydroxyl group, an amino group, or an acid group is anhydrous. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (h2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins.
Among the thermosetting agents (h2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter, may be abbreviated as "DICY") and the like.

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.
The thermosetting agent (h2) having an unsaturated hydrocarbon group is, for example, a compound in which a part of the hydroxyl group of the phenol resin is replaced with a group having an unsaturated hydrocarbon group, which is not suitable for the aromatic ring of the phenol resin. Examples thereof include compounds in which a group having a saturated hydrocarbon group is directly bonded.
The unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the epoxy resin having the unsaturated hydrocarbon group described above.

When a phenolic curing agent is used as the thermosetting agent (h2), the thermosetting agent (h2) preferably has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet. ..

Among the thermosetting agents (h2), the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene phenol resin, and aralkylphenol resin is preferably 300 to 30,000. It is more preferably 400 to 10000, and particularly preferably 500 to 3000.
The molecular weight of the non-resin component such as biphenol and dicyandiamide in the thermosetting agent (h2) is not particularly limited, but is preferably 60 to 500, for example.

As the thermosetting agent (h2), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

When the thermosetting component (h) is used, the content of the thermosetting agent (h2) in the protective film forming composition (IV-1) and the protective film forming film is 100, which is the content of the epoxy resin (h1). It is preferably 0.01 to 20 parts by mass with respect to the mass part.

When the thermosetting component (h) is used, the content of the thermosetting component (h) (for example, epoxy resin (h1) and heat) in the protective film forming composition (IV-1) and the protective film forming film. The total content of the curing agent (h2)) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the content of the polymer (b) having no energy ray-curable group.

[Curing accelerator (i)]
The curing accelerator (i) is a component for adjusting the curing rate of the protective film forming film.
Preferred curing accelerators (i) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-Phenyl-4-methylimidazole, 2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and other imidazoles; tributylphosphine, diphenylphosphine, triphenylphosphine and the like. Organic phosphins; tetraphenylphosphonium tetraphenylborate, tetraphenylborone salts such as triphenylphosphine tetraphenylborate and the like can be mentioned.

As the curing accelerator (i), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.
When the curing accelerator (i) is used, the content of the protective film forming composition (IV-1) and the curing accelerator (i) of the protective film forming film is not particularly limited, and depends on the components to be used in combination. It may be selected as appropriate.

[General-purpose additive (z)]
The general-purpose additive (z) may be a known one and may be arbitrarily selected depending on the intended purpose, and is not particularly limited, but preferred ones are, for example, plasticizers, antistatic agents, antioxidants, gettering agents and the like. Can be mentioned.

The general-purpose additive (z) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one kind, two or more kinds, and when two or more kinds, those The combination and ratio can be selected arbitrarily.
When the general-purpose additive (z) is used, the content of the protective film-forming composition (IV-1) and the general-purpose additive (z) of the protective film-forming film is not particularly limited and may be appropriately selected depending on the intended purpose. do it.

[solvent]
The protective film forming composition (IV-1) preferably further contains a solvent. The composition for forming a protective film (IV-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred ones are, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol. Examples thereof include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond).
The solvent contained in the protective film forming composition (IV-1) may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The solvent contained in the protective film-forming composition (IV-1) is methyl ethyl ketone, toluene, ethyl acetate or the like from the viewpoint that the components contained in the protective film-forming composition (IV-1) can be mixed more uniformly. Is preferable.

<< Manufacturing method of protective film forming composition >>
A protective film-forming composition such as the protective film-forming composition (IV-1) can be obtained by blending each component for constituting the protective film-forming composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, the solvent may be mixed with any compounding component other than the solvent and diluted in advance, or any compounding component other than the solvent may be diluted in advance. You may use it by mixing the solvent with these compounding components without leaving.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

◎ Manufacturing Method of Semiconductor Device In the method for manufacturing a semiconductor device of the present invention, the semiconductor chip with a protective film is obtained by the method for manufacturing a semiconductor chip with a protective film of the present invention, and then the semiconductor chip with a protective film is used. It has a pulling step of pulling away from the support sheet.

According to the method for manufacturing a semiconductor device of the present invention, even if the semiconductor chip with a protective film is pulled up from the support sheet by pushing up with a pin, it is possible to suppress the remaining of the push-up mark by the pin on the protective film. This is due to the high elastic modulus of the protective film provided on the back surface of the semiconductor chip.
That is, the method for manufacturing a semiconductor device of the present invention is suitable for pulling the semiconductor chip with a protective film away from the support sheet by pushing it up with a pin in the pulling step.

FIG. 4 is a cross-sectional view for schematically explaining one embodiment of the pulling step in the method for manufacturing a semiconductor device of the present invention. Here, the case where the processed laminated structure 101'shown in FIG. 1 is used will be described. In FIG. 4, only the configuration related to the processed laminated structure 101'is cross-sectionally displayed.

In the pulling step, for example, as shown in FIG. 4, a pin (projection) 70 is projected from a push-up portion (not shown) in a semiconductor device manufacturing apparatus, and the tip portion of the pin 70 is used with respect to the support sheet 10. , A force is applied from the base material 11 side. In this way, the pin 70 pushes up the semiconductor chip 8 with the protective film by applying a force to the semiconductor chip 8 with the protective film through the support sheet 10. Further, the semiconductor chip 8 with the protective film is pulled up by the pulling means 71 in the semiconductor device manufacturing apparatus, so that the semiconductor chip 8 with the protective film is separated (picked up) from the support sheet 10. Here, the pulling direction of the semiconductor chip 8 with a protective film is indicated by an arrow II. Examples of the pulling means 71 include a vacuum collet.

The pushing conditions such as the protruding amount (pushing amount), the protruding speed (pushing speed), and the holding time (lifting waiting time) of the protruding state of the pin 70 may be appropriately adjusted and are not particularly limited. The number of pins 70 to be projected with respect to one semiconductor chip 8 with a protective film is not particularly limited, and may be, for example, one or a plurality of pins 70, which may be appropriately selected.

In this step, the protective film 131'in which a force is applied through the support sheet 10 by the pin 70 has a high elastic modulus. Therefore, on the surface 131b'on the support sheet 10 side of the protective film 131', the residual push-up marks by the pins 70 are suppressed.

Further, since the elastic modulus of the protective film 131'is high, the semiconductor chip 8 with the protective film is prevented from adhering to the storage portion by the protective film 131' during storage.

Here, the pulling step when the processed laminated structure 101'shown in FIG. 1 is used has been described, but for example, when another processed laminated structure such as that shown in FIG. 3 is used, it is also possible to use. The pulling step can be performed in the same manner.

In the method for manufacturing a semiconductor device of the present invention, the semiconductor device may be manufactured by the same method as the conventional method thereafter. For example, a separated (picked up) semiconductor chip with a protective film is used, and this is flip-chip connected to the circuit surface of the substrate to form a semiconductor package. Then, the target semiconductor device may be manufactured by using this semiconductor package.

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

The components used in the production of the protective film forming composition are shown below.
[Energy ray curable component (a)]
(A2) -1: Tricyclodecanemethyloldiacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., bifunctional UV curable compound, molecular weight 304)
[Polymer without energy ray-curable group (b)]
(B) -1: Copolymerization of methyl acrylate (hereinafter abbreviated as "MA") (85 parts by mass) and -2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass). Acrylic resin (weight average molecular weight 400,000, glass transition temperature 8 ° C).
[Photopolymerization Initiator (c)]
(C) -1: 2- (Dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (BASF's "Irgacure (registered trademark) 369")
(C) -2: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (BASF's "Irgacure" (registered) Trademark) OXE02 ")
[Filler (d)]
(D) -1: Silica filler (Admatex "SC2050MA", surface-modified with an epoxy compound, average particle size 0.5 μm)
[Coupling agent (e)]
(E) -1: 3-glycidoxypropyltrimethoxysilane (3-glycidyloxypropyltrimethoxysilane) (silane coupling agent, "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd., methoxy equivalent 12.7 mmol / g, molecular weight 236 .3)
[Colorant (g)]
(G) -1: 32 parts by mass of phthalocyanine blue dye (Pigment Blue 15: 3), 18 parts by mass of isoindolinone yellow dye (Pigment Yellow 139), and 50 parts by mass of anthraquinone red dye (Pigment Red 177). A pigment obtained by mixing and pigmenting so that the total amount of the above three dyes / the amount of styrene acrylic resin = 1/3 (mass ratio).
[Thermosetting component (h)]
-Epoxy resin (h1)
(H1) -1: Bisphenol A type epoxy resin ("JER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194 g / eq)
(H1) -2: Bisphenol A type epoxy resin ("JER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800-900 g / eq)
(H1) -3: Dicyclopentadiene type epoxy resin ("Epiclon HP-7200HH" manufactured by DIC Corporation, epoxy equivalent 255-260 g / eq)
・ Thermosetting agent (h2)
(H2) -1: Dicyandiamide (thermally active latent epoxy resin curing agent, "ADEKA Hardener EH-3636AS" manufactured by ADEKA, active hydrogen amount 21 g / eq)
[Curing accelerator (i)]
(I) -1: 2-Phenyl-4,5-dihydroxymethylimidazole ("Curesol 2PHZ" manufactured by Shikoku Chemicals Corporation)

The stretch ratio of the base material was measured by the following method.
That is, first, the base material is cut into a size of 22 mm in short side and 110 mm in long side so that the short side is in the CD direction and the long side is in the MD direction, and this is a test piece for measuring the expansion / contraction rate in the MD direction. And said. Of the 110 mm length, 100 mm at the center in the length direction is marked on the test piece as the distance between measurements, and each end of the test piece in the length direction (5 mm portion at the end) has a mass of 2.2 g. I attached the clip.

The test piece was then suspended in the oven using one clip. The load on the test piece at this time was the mass of the lower clip, that is, 0.1 g / mm. The test piece was heated in the oven at 130 ° C. and 30% RH (relative humidity) for 2 hours, and then the test piece was taken out from the oven and cooled to 23 ° C. Next, the marked distance between measurements of the test piece was measured again, and the expansion / contraction rate (%) of the base material in the MD direction was calculated according to the following formula.
Elasticity (%) = (distance between measurements after heating / distance between measurements before heating) x 100

Separately, the base material is cut into a size of 22 mm on the short side and 110 mm on the long side so that the short side is in the MD direction and the long side is in the CD direction, and this is used as a test piece for measuring the expansion / contraction rate in the CD direction. did. Using this test piece, the stretch ratio (%) in the CD direction of the base material was calculated by the same method as in the case of the test piece for measuring the stretch ratio in the MD direction.

The tensile elastic modulus of the base material was measured by the following method.
That is, first, the base material was cut into a size of 15 mm × 140 mm, and this was used as a test piece.
Then, according to JIS K7127: 1999, the tensile elastic modulus (Young's modulus) of the test piece at 23 ° C. was measured. Specifically, the test piece is installed in a tensile tester (“Autograph AG-IS 500N” manufactured by Shimadzu Corporation), the distance between chucks is set to 100 mm, and then the test piece is pulled at a speed of 200 mm / min. A test was conducted and the tensile elastic modulus (MPa) was measured. The tensile modulus was measured in both the MD and CD directions of the substrate.

<Manufacturing of composite sheet for forming protective film>
[Manufacturing Example 1]
(Production of composition for forming a protective film (IV-1))
Energy ray curable component (a2) -1, polymer (b) -1 having no energy ray curable group, photopolymerization initiator (c) -1, photopolymerization initiator (c) -2, filler ( d) -1, the coupling agent (e) -1 and the colorant (g) -1 are dissolved or dispersed in methyl ethyl ketone so that their contents (solid content, parts by mass) are as shown in Table 1. Then, the composition (IV-1) for forming a protective film having a solid content concentration of 50% by mass was prepared by stirring at 23 ° C. In addition, the description of "-" in the column of the contained component in Table 1 means that the protective film forming composition (IV-1) does not contain the component.

(Manufacturing of protective film forming film)
The protective film forming composition (IV-1) obtained above is applied to the peeled surface of the peeled film obtained by peeling one side of the polyethylene terephthalate film by silicone treatment, and the temperature is 120 ° C. By drying for minutes, an energy ray-curable protective film-forming film having a thickness of 15 μm was produced.

(Production of Adhesive Composition (I-2))
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate-based cross-linking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (6.6 parts by mass, solid content), and photopolymerization initiator (2). -Hyrodoxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one, BASF "Irgacure (registered trademark) 127") (3 An energy ray-curable pressure-sensitive adhesive composition (I-2) having a solid content concentration of 30% by mass was prepared, which contained 0.0 parts by mass (solid content) and further contained methyl ethyl ketone as a solvent. The acrylic polymer includes -2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (80 parts by mass) and -2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (20 mass). 2-Methacloyloxyethyl isocyanate (21.4 parts by mass, the amount of isocyanate group is 80 mol% with respect to 100 mol% of hydroxyl group in HEA) is reacted with the prepolymer obtained by copolymerizing (part). This is an energy ray-curable acrylic polymer having a weight average molecular weight of 1100000.

(Manufacturing of support sheet)
The pressure-sensitive adhesive composition (I-2) obtained above is applied to the peeled surface of the peeled film obtained by peeling one side of the polyethylene terephthalate film by silicone treatment, and heated at 120 ° C. for 2 minutes. By drying, an energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 μm was formed.
Next, a flexible polypropylene film (thickness 80 μm) was attached to the exposed surface of the pressure-sensitive adhesive layer to manufacture a support sheet.

The flexible polypropylene film used here had a stretch ratio of 230% in the MD direction and a stretch ratio of 130% in the CD direction. The tensile elastic modulus in the MD direction was 160 MPa, and the tensile elastic modulus in the CD direction was 155 MPa.

(Manufacturing of composite sheet for forming protective film)
Next, the release film on the pressure-sensitive adhesive layer of the support sheet is removed, and the exposed surface of the protective film-forming film obtained above is attached to the surface of the exposed pressure-sensitive adhesive layer to form a base material and a pressure-sensitive adhesive layer. , A protective film-forming film and a release film were laminated in this order in the thickness direction to prepare a protective film-forming composite sheet. Table 2 shows the structure of the obtained composite sheet for forming a protective film.

[Manufacturing Example 2]
(Manufacturing of composition for forming protective film)
Polymer (b) -1, filler (d) -1, coupling agent (e) -1, colorant (g) -1, epoxy resin (h1) -1, epoxy without energy ray curable group Table 1 shows the contents (solid content, parts by mass) of the resin (h1) -2, the epoxy resin (h1) -3, the thermosetting agent (h2) -1, and the curing accelerator (i) -1. A composition for forming a thermosetting protective film having a solid content concentration of 50% by mass was prepared by dissolving or dispersing in methyl ethyl ketone so as to have a value and stirring at 23 ° C.

(Manufacturing of protective film forming film)
Thermosetting protection is carried out in the same manner as in Production Example 1 except that the thermosetting protective film forming composition obtained above is used instead of the protective film forming composition (IV-1). A film for forming a film was produced.

(Manufacturing of adhesive composition and support sheet)
The pressure-sensitive adhesive composition and the support sheet were produced by the same method as in Production Example 1.

(Manufacturing of composite sheet for forming protective film)
Next, the release film on the pressure-sensitive adhesive layer of the support sheet is removed, and the exposed surface of the heat-curable protective film forming film obtained above is attached to the surface of the exposed pressure-sensitive adhesive layer to form a base material. , The pressure-sensitive adhesive layer, the protective film-forming film, and the release film were laminated in this order in the thickness direction to prepare a protective film-forming composite sheet. Table 2 shows the structure of the composite sheet for forming the protective film.

[Manufacturing Example 3]
(Manufacturing of protective film forming composition and protective film forming film)
A protective film-forming composition and a protective film-forming film were produced in the same manner as in Production Example 2.

(Manufacturing of Adhesive Composition (I-4))
It contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based cross-linking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass, solid content), and methyl ethyl ketone as a solvent. A non-energy ray-curable pressure-sensitive adhesive composition (I-4) having a solid content concentration of 30% by mass was prepared. The acrylic polymer is obtained by copolymerizing 2EHA (60 parts by mass), methyl methacrylate (hereinafter abbreviated as "MMA") (30 parts by mass), and HEA (10 parts by mass), and has a weight average molecular weight. Is 600,000.

(Manufacturing of support sheet)
The non-energy ray-curable pressure-sensitive adhesive composition (I-4) obtained above was applied to the peeled surface of the peeled film obtained by peeling one side of the polyethylene terephthalate film by silicone treatment. By heating and drying at 120 ° C. for 2 minutes, a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 5 μm was formed.
Next, a heat-resistant polypropylene film (thickness 80 μm) was attached to the exposed surface of the pressure-sensitive adhesive layer to manufacture a support sheet.

The heat-resistant polypropylene film used here had a stretch ratio of 98.2% in the MD direction and a stretch ratio of 99.5% in the CD direction. The tensile elastic modulus in the MD direction was 470 MPa, and the tensile elastic modulus in the CD direction was 490 MPa.

(Manufacturing of composite sheet for forming protective film)
Next, the release film on the pressure-sensitive adhesive layer of the support sheet is removed, and the exposed surface of the protective film-forming film obtained above is attached to the surface of the exposed pressure-sensitive adhesive layer to form a base material and a pressure-sensitive adhesive layer. , A protective film-forming film and a release film were laminated in this order in the thickness direction to prepare a protective film-forming composite sheet. Table 2 shows the structure of the obtained composite sheet for forming a protective film.

[Example 1]
<Manufacturing of semiconductor chips with protective film>
A semiconductor chip with a protective film was manufactured by the above-mentioned manufacturing method (1) according to the procedure shown below.

(Laminate structure forming process)
A laser saw is applied to a 12-inch silicon wafer (thickness 300 μm) in which a back grind tape is attached to the circuit forming surface and the back surface opposite to the circuit forming surface is a # 2000 grinding surface. ("DFL7360" manufactured by Disco Corporation) was used to irradiate a laser beam having a wavelength of 1064 nm to form a modified layer inside the silicon wafer.
Next, using a tape mounter (“ADWILL RAD-2700” manufactured by Lintec Corporation), the protective film forming film of the protective film forming composite sheet obtained in Production Example 1 was heated to 70 ° C. to form the protective film. A laminated structure was formed by attaching a composite sheet for forming a protective film to the ground surface of the silicon wafer via a film.

(Expanding process)
After mounting the ring frame on the laminated structure obtained above, remove the back grind tape, cool the protective film forming film at 0 ° C., and use an expander (Disco "DDS2300") to push up the speed. By pushing up the table under the conditions of 20 mm / sec and a push-up amount of 20 mm, the laminated structure was expanded in the surface direction of the protective film forming film. As a result, the film for forming the protective film was cut, and the silicon wafer was divided at the site of the modified layer to obtain a plurality of semiconductor chips having a size of 3 mm × 3 mm.

(Protective film forming process)
The cut protective film-forming film was irradiated with ultraviolet rays under the conditions of an illuminance of 230 mW / cm ² and a light intensity of 170 mJ / cm ² to form a protective film, thereby forming a semiconductor chip with a protective film.

<Evaluation of support sheet and semiconductor chip with protective film>
(Heat shrinkability (restorability of support sheet))
After the above-mentioned expanding step, the peripheral portion was heated by blowing hot air onto the peripheral portion of the support sheet under the conditions of a temperature of 220 ° C. and a rotation speed of 5 mm / ° using a dryer. Next, the peripheral edge of the support sheet after heating was visually observed, and it was confirmed whether or not the slack generated in the support sheet by the expansion was eliminated by the shrinkage of the support sheet due to the heating, and the evaluation was made according to the following criteria. The results are shown in Table 2.
◯: The slack is eliminated.
X: The slack is not eliminated, and it is impossible to transport or store the semiconductor chip with a protective film after expansion.

(Remaining suppression of push-up marks by pins on the protective film)
At the time of the above-mentioned expanding step and the evaluation of the heat shrinkability, no problem was observed. Using the processed laminated structure, an attempt was made to pick up the semiconductor chip with a protective film by the procedure shown below.
That is, using a device in which a No. 5 needle is set as a pin used for pushing up on a push-pull gauge (“MODEL-RE” manufactured by Aiko Engineering Co., Ltd.), the pushing amount is set to 1.5 mm, and a semiconductor with a protective film is passed through the support sheet. I pushed up the tip. Then, the protective film was visually observed to confirm the presence or absence of needle marks, and the evaluation was made according to the following criteria. The results are shown in Table 2.
◯: There is no needle mark.
X: There is a needle mark.

[Example 2]
<Manufacturing of semiconductor chips with protective film>
(Laminate structure forming process)
A laminated structure was formed in the same manner as in Example 1.

(Protective film forming process)
The protective film-forming film of the laminated structure obtained above was irradiated with ultraviolet rays under the conditions of an illuminance of 230 mW / cm ² and a light intensity of 170 mJ / cm ² to form a protective film.

(Expanding process)
Instead of the laminated structure provided with the protective film forming film described above, the laminated structure obtained above after forming the protective film is used, and the protective film forming film is cooled at 0 ° C. at the time of expansion. Instead, the protective film was cut in the same manner as in Example 1 except that the temperature of the protective film was set to 30 ° C., and the silicon wafer was divided at the site of the modified layer to have a size of 3 mm. A plurality of semiconductor chips of × 3 mm were used, and a semiconductor chip with a protective film was obtained.

<Evaluation of semiconductor chips with support sheets and protective film forming films>
(Heat shrinkability (restorability of support sheet) and suppression of residual push-up marks by pins on protective film forming film)
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 1]
<Manufacturing of semiconductor chips with film for forming protective film>
A semiconductor chip with a protective film-forming film was manufactured by the procedure shown below by the conventional method described with reference to FIG.

A laminated structure is formed by the same method as in Example 1 except that the protective film-forming composite sheet obtained in Production Example 2 is used instead of the protective film-forming composite sheet obtained in Production Example 2. did.
Next, in the same manner as in Example 1, the obtained laminated structure was expanded, the protective film-forming film was cut, and the silicon wafer was divided at the site of the modified layer to form a plurality of 3 mm × 3 mm in size. Obtained three semiconductor chips.
From the above, a semiconductor chip with a film for forming a protective film was obtained.

<Evaluation of semiconductor chips with support sheets and protective film forming films>
(Heat shrinkability (restorability of support sheet) and suppression of residual push-up marks by pins on protective film forming film)
Evaluation was performed in the same manner as in Example 1. In this comparative example, since the protective film forming film was not cured, the residual suppression of the push-up marks by the pins was performed not with the protective film but with the protective film forming film. The results are shown in Table 2.

[Comparative Example 2]
<Manufacturing of semiconductor chips with protective film>
A semiconductor chip with a protective film was manufactured by the procedure shown below by the conventional method described with reference to FIG.

A laminated structure is formed by the same method as in Example 1 except that the protective film-forming composite sheet obtained in Production Example 3 is used instead of the protective film-forming composite sheet obtained in Production Example 3. did.
Next, the obtained laminated structure was heated at 130 ° C. for 2 hours to cure the protective film-forming film to form a protective film.
Next, this lamination was carried out in the same manner as in Example 1 except that the laminated structure after the protective film forming film was cured was used instead of the laminated structure before the protective film forming film was cured. The structure was expanded, the protective film was cut, and the silicon wafer was divided at the site of the modified layer to obtain a plurality of semiconductor chips having a size of 3 mm × 3 mm.
From the above, a semiconductor chip with a protective film was obtained.

<Evaluation of support sheet and semiconductor chip with protective film>
(Heat shrinkability (restorability of support sheet) and suppression of residual push-up marks by pins on the protective film)
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

(Heat resistance of support sheet)
The placement position of the protective film forming composite sheet was recorded after mounting the ring frame on the laminated structure and before the curing of the protective film forming film by heating described above. Next, the protective film-forming film is cured by heating (formation of the protective film), the protective film-forming film is cooled, and before the laminated structure is expanded, the protective film-forming composite is formed. The placement position of the sheet was recorded. Then, from the recording of these arrangement positions, the amount of subduction (slack amount) of the protective film-forming composite sheet due to the curing of the protective film-forming film was calculated and evaluated according to the following criteria. The results are shown in Table 2. The description of "-" in the evaluation result column in Table 2 means that the item has not been evaluated.
◯: The amount of subduction is less than 0.5 mm.
X: The amount of subduction is 0.5 mm or more.

As is clear from the above results, in Examples 1 and 2, since the protective film forming film was not heat-cured but cured by energy ray irradiation, the support sheet did not loosen immediately after curing. .. On the other hand, the slack generated in the support sheet by the expanding step was eliminated by heating the peripheral portion of the support sheet described above, and the heat shrinkability (restorability of the support sheet) was good. This is because a flexible base material is used. Further, in Examples 1 and 2, the elastic modulus of the protective film was high, so that the residual push-up marks by the pins were suppressed. Then, in Example 1, after the expanding step, the protective film forming film was sufficiently cut at a target location, and the semiconductor wafer was also satisfactorily divided. In Example 2, after the expanding step, the protective film was sufficiently cut at a target location, and the semiconductor wafer was also satisfactorily divided. In Examples 1 and 2, since the protective film forming film is not heat-cured, the support sheet (base material) does not need to have heat resistance, and the heat resistance of the support sheet has not been evaluated.

On the other hand, in Comparative Example 1, since the protective film forming film was not thermoset, the support sheet did not loosen at the stage before expansion. Further, as in the case of Example 1, since a flexible base material was used, the heat shrinkability was good. However, since the protective film-forming film was not cured and the protective film was not formed, it was not possible to suppress the residual push-up marks due to the pins in the protective film-forming film having a low elastic modulus. In Comparative Example 1, after the expansion, the protective film-forming film was sufficiently cut at a target location, and the semiconductor wafer was also satisfactorily divided. In Comparative Example 1, since the protective film forming film is not heat-cured as in Example 1, the support sheet (base material) does not need to have heat resistance, and the heat resistance of the support sheet is not required. Has not been evaluated.

In Comparative Example 2, the protective film-forming film was thermoset, but since a heat-resistant base material was used, the support sheet did not loosen immediately after curing. On the other hand, the slack generated in the support sheet by the expansion was not eliminated by the heating of the peripheral portion of the support sheet described above, and the heat shrinkability was poor. As a result, the subsequent steps cannot be performed, and the suppression of residual push-up marks by the pins on the protective film has not been evaluated. In Comparative Example 2, the heat resistance of the support sheet was good.

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

10 ... Support sheet, 11 ... Base material, 11a ... One surface of base material, 12 ... Adhesive layer, 12a ... One surface of adhesive layer, 13 ... Protection Film forming film, 13a ... One surface of protective film forming film, 131 ... Protective film forming film after cutting, 131', 132 ... Protective film, 132a ... Surface of protective film , 132'... protective film after cutting, 101 ... laminated structure, 102 ... laminated structure after forming protective film, 8 ... semiconductor chip, 81'... modified semiconductor wafer Quality layer, 8'... semiconductor wafer

Claims (5)

An energy ray-curable protective film forming film is provided on the support sheet, a semiconductor wafer is provided on the protective film forming film, and a modified layer is formed inside the semiconductor wafer. Laminated structure forming process to form a structure and
After the laminated structure forming step,
A protective film forming step of irradiating the protective film forming film with energy rays to form a protective film,
The laminated structure after forming the protective film is expanded toward the surface of the protective film to cut the protective film, and the semiconductor wafer is divided at the site of the modified layer to form a plurality of protective films. With an expanding process to obtain a semiconductor chip with
The protective film-forming film comprises a compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000, a polymer (b) having no energy ray-curable group, and a filler (d). Contains,
The compound (a2) is an acrylate-based compound having a (meth) acryloyl group as the energy ray-curable group, and the polymer (b) is an acrylic-based polymer.
The total content of the compound (a2) and the polymer (b) of the protective film forming film is 15 to 70% by mass, and the content of the filler (d) of the protective film forming film is , 7-78% by mass,
A method for producing a semiconductor chip with a protective film, which expands the laminated structure at room temperature or while heating the protective film in the expanding step. An energy ray-curable protective film forming film is provided on the support sheet, a semiconductor wafer is provided on the protective film forming film, and a modified layer is formed inside the semiconductor wafer. Laminated structure forming process to form a structure and
After the laminated structure forming step,
The laminated structure is expanded toward the surface of the protective film forming film to cut the protective film forming film, and the semiconductor wafer is divided at the site of the modified layer to form a plurality of semiconductor chips. The expanding process to obtain and
It has, or has, a protective film forming step of obtaining a semiconductor chip with a protective film by irradiating the protective film forming film after cutting with energy rays to form the protective film.
A protective film forming step of irradiating the protective film forming film with energy rays to form a protective film,
The laminated structure after forming the protective film is expanded toward the surface of the protective film to cut the protective film, and the semiconductor wafer is divided at the site of the modified layer to form a plurality of protective films. With an expanding process to obtain a semiconductor chip with
The support sheet has an adhesive layer provided on a base material.
For a test piece of the base material having a length of 22 mm in the CD direction and a length of 110 mm in the MD direction, the test piece is suspended at one of both ends in the MD direction, and a load of 0.1 g is applied to the other. When / mm was added and the test piece was heated at 130 ° C. and 30% RH for 2 hours and cooled to 23 ° C., the expansion / contraction rate of the test piece in the MD direction became 100 to 250%.
Regarding the test piece of the base material having a length of 22 mm in the MD direction and a length of 110 mm in the CD direction, the test piece is suspended at one of both ends in the CD direction, and a load of 0.1 g is applied to the other. When / mm was added and the test piece was heated at 130 ° C. and 30% RH for 2 hours and cooled to 23 ° C., the expansion / contraction rate of the test piece in the CD direction became 100 to 150%.
When the tensile elastic modulus at 23 ° C. was measured for the test piece of the base material having a size of 15 mm × 140 mm in accordance with JIS K7127: 1999, the tensile elastic modulus in the MD direction and the CD direction of the test piece was determined. A method for manufacturing a semiconductor chip with a protective film, both of which are 100 to 400 MPa. Prior to the laminated structure forming step, further
The semiconductor wafer before the protective film forming film is provided is irradiated with a laser beam so as to focus on the focal point set inside the semiconductor wafer, and the modified layer is formed inside the semiconductor wafer. The method for producing a semiconductor chip with a protective film according to claim 1 or 2, which comprises a modified layer forming step. The support sheet has an adhesive layer provided on a base material.
The method for manufacturing a semiconductor chip with a protective film according to any one of claims 1 to 3, wherein the protective film forming film is provided in direct contact with the pressure-sensitive adhesive layer. After obtaining the semiconductor chip with a protective film by the method for manufacturing a semiconductor chip with a protective film according to any one of claims 1 to 4.
A method for manufacturing a semiconductor device, comprising a pulling step of pulling the semiconductor chip with a protective film away from the support sheet.

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