JP2018056282A - Manufacturing method of semiconductor chip with protection film, and manufacturing method of semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a semiconductor chip with a protection film, which has good breaking property of an expanded protection film or a film for forming the protection film, and support property of a semiconductor wafer on a support sheet, and which can suppress remaining of a pick-up trace due to a pin in the protection film when picking up by the pin and separating the semiconductor chip with the protection film.SOLUTION: A semiconductor chip 8 with a protection film is formed by a method of providing an energy line curable protection film formation film 13 onto a support sheet 10, providing a semiconductor wafer 8' onto the film 13, forming a laminate structure 101 in which a modified layer 81' is formed in an inner part of the semiconductor wafer 8', cutting the film 13 by expanding the laminate structure 101 to a direction of a front surface 13a of the film 13 and dividing the semiconductor wafer 8' at a position of the modified layer 81', obtaining the plurality of semiconductor chips 8, and applying an energy line to the film 131 to be cut and forming a protection film 131'.SELECTED DRAWING: Figure 1

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.

  2. Description of the Related Art In recent years, semiconductor devices using a mounting method called a so-called face down method have been manufactured. In the face-down method, a semiconductor chip having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. For this reason, the back surface of the semiconductor chip opposite to the circuit formation surface may be exposed.

  A resin film containing an organic material is formed as a protective film on the exposed back surface of the semiconductor chip, and may be taken into the 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 the protective film-forming film is usually provided on a support sheet. It is used in the state of a composite sheet for forming a protective film. In the protective film forming composite sheet, the protective film forming film can form a protective film by curing, and the support sheet can be used as a dicing sheet, and the protective film forming film and the dicing sheet are integrated. It is possible that And as a film for protective film formation, the thermosetting film, ie, the film which forms a protective film by thermosetting, is known.

FIG. 5 is a cross-sectional view for schematically explaining a method of manufacturing a semiconductor chip with a protective film when a thermosetting protective film-forming film is used.
In this manufacturing method, first, as shown in FIG. 5A, a semiconductor wafer 8 ′ in which a modified layer 81 ′ is formed beforehand is applied to a protective film forming film 931 of a protective film forming composite sheet 901. Keep it on top. The protective film-forming composite sheet 901 is obtained by providing a protective film-forming film 931 on the support sheet 10. Next, as shown in FIG. 5B, the protective film-forming film 931 is cured by heating to form a protective film 931 ′. Next, the semiconductor wafer 8 ′ is expanded together with the protective film-forming composite sheet 901 ′ after the formation of the protective film 931 ′ in the surface direction of the protective film 931 ′ (in the direction indicated by the arrow I in the figure). As shown in FIG. 5C, the protective film 931 ′ is cut and the semiconductor wafer 8 ′ is divided at the modified layer 81 ′ to obtain a plurality of semiconductor chips 8 with a protective film. In FIG. 5, reference numeral 9310 ′ indicates the protective film after cutting.
As shown here, a method for forming a modified layer inside a semiconductor wafer and dividing the semiconductor wafer at the portion of the modified layer is as follows. This method has advantages over the dividing method, and its wide utilization 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 the protective film, the support sheet 10 needs to have heat resistance. The elastic modulus of the sheet 10 needs to be increased. Here, the support sheet 10 is shown in which a pressure-sensitive adhesive layer 12 is provided on a substrate 11, and in this case, it is particularly necessary to increase the elastic modulus of the substrate 11. However, if the elastic modulus of the support sheet 10 is high, the support sheet 10 (composite sheet 901 ′ for protective film formation) becomes difficult to expand, and thus the protective film 931 ′ cannot be sufficiently cut.
Further, when the protective film-forming film 931 is heat-cured, the protective film 931 ′ contracts due to the curing, and the division proceeds in advance at least in 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 for obtaining a semiconductor chip by dividing a semiconductor wafer, a method in which the protective film-forming film is not cured in the process until the semiconductor chip is obtained may be considered. In this method, not a semiconductor chip with a protective film but a semiconductor chip with a protective film-forming film is manufactured. Also in such a case, the protective film-forming film is usually provided on a support sheet and used in the state of a 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, similarly to the above, as shown in FIG. 6A, a semiconductor wafer 8 ′ in which a modified layer 81 ′ is formed in advance is protected by a composite sheet 902 for forming a protective film. It is provided on the film forming film 932. The protective film-forming composite sheet 902 is obtained by providing a protective film-forming film 932 on the support sheet 10. Next, without curing the protective film forming film 932, the semiconductor wafer 8 ′ is 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). Then, 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 modified layer 81 ′. A semiconductor chip 8 with a film is obtained. In FIG. 6, the code | symbol 9320 shows the film for protective film formation after a cutting | disconnection. In this manufacturing method, the protective film-forming film 932 may be either a curable type or a non-curable type, and in the case of the curable type, for example, any of thermosetting and energy ray curable can be used. However, the curable protective film-forming film is used without being cured.

In this manufacturing method, since the protective film-forming film 932 is not cured, the heating step is unnecessary, and the support sheet 10 is not required to have heat resistance, and the elastic modulus of the support sheet 10 as described above is increased. Problems associated with increasing the height can be avoided, and the supportability of the semiconductor wafer 8 ′ on the support sheet 10 does not deteriorate.
A method of cutting without curing a resin film containing an organic material, such as this protective film-forming film, is disclosed in the case of using a die bond film as a resin film to be attached to a semiconductor wafer (Patent Document 1). reference).

JP 2011-171588 A

  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 formed in the obtained semiconductor chip with the protective film-forming film. Since it is cured, its elastic modulus is low. As a result, when the semiconductor chip with the protective film forming film is pushed up by the pins according to the conventional method and pulled away from the support sheet and picked up, the pushing marks by the pins are likely to remain in the protective film forming film. It should be noted that such a push-up mark by the pin can remain even in a protective film having a low elastic modulus. From such a viewpoint, it is desirable that the semiconductor chip is provided with a sufficiently hardened protective film at the time of pickup.

  Accordingly, 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 that has been cut off at a target location, on the back surface of the semiconductor chip. Or when the cutting ability 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, when 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 remaining of a push-up mark due to a pin in the protective film.

  In order to solve the above problems, the present invention provides an energy ray-curable protective film-forming film on a support sheet, and a semiconductor wafer is provided on the protective film-forming film. In the laminated structure forming step of forming a laminated structure in which a modified layer is formed, and after the laminated structure forming step, the laminated structure is expanded in the surface direction of the protective film forming film, The protective film forming film is cut and the semiconductor wafer is divided at the modified layer to obtain a plurality of semiconductor chips, and the protective film forming film is irradiated with energy rays after cutting. Forming a protective film to obtain a semiconductor chip with a protective film, or having an energy in the protective film-forming film A protective film forming step of forming a protective film by irradiating the protective film; and expanding the laminated structure after forming the protective film in a surface direction of the protective film, cutting the protective film, and forming the modified layer And an expanding step of dividing the semiconductor wafer at a portion to obtain a plurality of semiconductor chips with protective films.

The method for manufacturing a semiconductor chip with a protective film according to the present invention has a focus set in the semiconductor wafer before the layered structure forming step and before the protective film forming film is provided. It is preferable to have a modified layer forming step of forming the modified layer inside the semiconductor wafer by irradiating a laser beam so as to be focused.
In the method for producing a semiconductor chip with a protective film of the present invention, the support sheet is a substrate in which an adhesive layer is provided, and the protective film-forming film is in direct contact with the adhesive layer. Are preferably provided.
Further, the present invention provides a method for manufacturing a semiconductor device, comprising: a step of separating the semiconductor chip with a protective film from the support sheet after obtaining the semiconductor chip with a protective film by the method for manufacturing the semiconductor chip with a protective film. I will provide a.

  According to the present invention, there is provided a method for manufacturing a semiconductor chip with a protective film, which is formed by curing a protective film-forming film and has been cut at a target location on the back surface of the semiconductor chip, and is protected by expanding. When the film or the film for forming the protective film has good cutting properties and the support of the semiconductor wafer on the support sheet used at the time of expansion, when the semiconductor chip with protective film is pulled away from the support sheet by pushing up with a pin There is provided a method of manufacturing a semiconductor chip with a protective film, which can suppress the remaining of a push-up mark due to a pin in the protective film.

It is sectional drawing for demonstrating typically one Embodiment of the manufacturing method of this invention. It is sectional drawing which shows typically the semiconductor wafer with which the back grind tape was affixed. It is sectional drawing for demonstrating other embodiment of the manufacturing method of this invention typically. It is sectional drawing for demonstrating typically one Embodiment of the separation process in the manufacturing method of the semiconductor device of this invention. It is sectional drawing for demonstrating typically the manufacturing method of the conventional semiconductor chip with a protective film at the time of using the composite sheet for protective film formation provided with the film for thermosetting protective film formation. It is sectional drawing for demonstrating typically the manufacturing method of the conventional semiconductor chip with a film for protective film formation at the time of using the composite sheet for protective film formation provided with the film for non-hardening type protective film formation.

In the method for producing 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. A laminated structure forming step of forming a laminated structure in which a modified layer is formed, and after the laminated structure forming step,
The laminated structure is expanded in the surface direction of the protective film forming film, the protective film forming film is cut, and the semiconductor wafer is divided at a portion of the modified layer, and a plurality of semiconductor chips are formed. And a protective film forming step of obtaining a semiconductor chip with a protective film by irradiating the film for forming the protective film after cutting with an energy ray to form a protective film (this method is described in the present specification). May be referred to as “manufacturing method (1)”), or
A protective film forming step of forming a protective film by irradiating the protective film forming film with an energy ray, and expanding the laminated structure after forming the protective film in a surface direction of the protective film, And the expanding step of dividing the semiconductor wafer at the portion of the modified layer to obtain a plurality of semiconductor chips with a protective film (this method is referred to as “manufacturing method (2) in this specification”). ”).
In the production method (1) and the production method (2) of the present invention, the order of the expansion and the formation of the protective film are different from each other.
Hereinafter, the manufacturing method of the semiconductor chip with a protective film of this invention is demonstrated in detail for every manufacturing method.

◎ Manufacturing method of semiconductor chip with protective film (Manufacturing method (1))
In the method for producing 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. A laminated structure forming step of forming a laminated structure in which a modified layer is formed inside the semiconductor wafer; and expanding the laminated structure in a surface direction of the protective film forming film. Cutting the protective film-forming film and dividing the semiconductor wafer at the modified layer to obtain a plurality of semiconductor chips, and applying energy rays to the protective film-forming film after cutting. A protective film forming step of obtaining a semiconductor chip with a protective film by irradiating to form a protective film.

  According to the production method (1) of the present invention, since the protective film-forming film is energy ray curable, heating is not necessary for forming the protective film, it does not have heat resistance as a support sheet, and has a low elastic modulus. Things can be used. Therefore, the support sheet can be easily expanded, and the protective film-forming film can be sufficiently cut. In addition, since heating is not required for forming the protective film, a decrease in supportability (sagging) on the support sheet of the semiconductor wafer is suppressed.

  Moreover, 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, in order to form the modified layer, there is no need to transmit the support sheet and the protective film forming film and irradiate the semiconductor wafer with laser light. There is no limitation. In addition, in order to increase the laser beam transmissivity, the smoothness of the surface of the outermost layer (for example, the exposed surface of the base material) on the side opposite to the side on which the protective film forming film is provided is improved. Therefore, it is possible to suppress the occurrence of blocking during storage of the support sheet.

  On the other hand, in the conventional method of dividing a semiconductor wafer by blade dicing or the like, for example, a part of the semiconductor wafer is cut away, so that the semiconductor wafer is lost by the amount cut off, 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 modified layer portion avoids the above-mentioned problems because the semiconductor wafer is not partially removed. This is advantageous.

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

Further, in this 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. The “semiconductor chip with protective film” means “semiconductor chip having a protective film after cutting on the back surface”.
Hereinafter, the production 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 one embodiment of the production method (1) of the present invention. In addition, in order to make the features of the present invention easy to understand, the drawings used in the following description may show the main parts in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

○ Laminated structure forming step In the laminated structure forming step of the production method (1), as shown in FIG. 1A, an energy ray curable protective film forming film 13 is provided on a 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 a pressure-sensitive adhesive layer 12 provided on a substrate 11, a protective film-forming film 13 is provided in direct contact with the pressure-sensitive 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 substrate 11, and the protective film-forming film 13 is provided on the one surface 12a of the pressure-sensitive adhesive layer 12. The semiconductor wafer 8 ′ is provided on one surface 13 a 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 the surface opposite to the circuit forming surface 8a' can be a ground surface generated by grinding as will be described later.

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

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

The thickness of the substrate is preferably 50 to 300 μm, and 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 adhesiveness to the semiconductor wafer 8 ′ or the semiconductor chip 8 described later can be achieved. More improved.
In this specification, “the thickness of the substrate” means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate. Means.

In order to improve the adhesiveness with the layer (here, for example, pressure-sensitive adhesive layer 12) provided thereon, the base material 11 is subjected to a roughening process such as a sand blast process, a solvent process, a corona discharge process, 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.
Moreover, the base material 11 may have a surface 11a that has been subjected to primer treatment.
In addition, the base material 11 prevents the base material 11 from adhering to other sheets or the base material 11 from adhering to the suction table when the antistatic coat layer and the semiconductor processing sheet are stacked and stored. It may have a layer or the like.

  The optical properties of the substrate 11 are not particularly limited as long as the effects of the present invention are not impaired. However, the substrate 11 preferably transmits laser light or energy rays.

  The substrate 11 is preferably highly flexible. By using such a base material 11, the support sheet 10 has a low elastic modulus, becomes easy to expand, and is advantageous for sufficiently cutting 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 looseness generated in the support sheet by the expanding process is eliminated by heating after the expanding process, and the good restorability of the supporting sheet ( Heat shrinkability).

From such a viewpoint, the base material 11 has an MD (Machine Direction) stretch rate of 50 to 300% and a CD (Cross Direction) stretch rate measured by the method described in the examples described later. Is preferably from 50 to 300%, more preferably from 100 to 250% in the MD direction and from 100 to 150% in the CD direction.
In the present specification, “MD direction” means a line direction for manufacturing the base material 11, and “CD direction” means a direction orthogonal to the MD direction, that is, a width direction for manufacturing the base material 11. means.

  Moreover, since the base material 11 is highly flexible, it becomes easier to pick up a semiconductor chip with a protective film, which will be described later. From such a point of view, the base material 11 preferably has a tensile modulus in the MD direction and the CD direction at 23 ° C. of 50 to 500 MPa, both measured by the method described in Examples described later, What is 400 MPa is more preferable.

  The substrate 11 can be manufactured by a known method. For example, the substrate 11 containing a resin 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 as or different from each other, and the combination of these layers is not particularly limited as long as the effects of the present invention are not impaired.

Although the thickness of the adhesive layer 12 can be suitably selected according to the objective, it is preferable that it is 1-100 micrometers, it is more preferable that it is 1-60 micrometers, and it is especially preferable that it is 1-30 micrometers.
In this specification, the “thickness of the pressure-sensitive adhesive layer” means the thickness of the whole pressure-sensitive adhesive layer. For example, the thickness of the pressure-sensitive adhesive layer composed of a plurality of layers means all layers constituting the pressure-sensitive adhesive layer. Means the total thickness.

  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 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, “energy beam” means an electromagnetic wave or charged particle beam having energy quanta, 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 ray source. The electron beam can be emitted by an electron beam accelerator or the like.
In this specification, “energy ray curable” means a property that cures when irradiated with energy rays, and “non-energy ray curable” means a property that does not cure even when irradiated 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 includes a plurality of layers, these layers may be the same or different from each other, and the combination of these layers is not particularly limited as long as the effects of the present invention are not impaired.

Although the thickness of the film 13 for protective film formation is not specifically limited, It is preferable that it is 1-50 micrometers, and it is more preferable that it is 3-40 micrometers. When the thickness of the protective film-forming film 13 is equal to or greater than the lower limit value, the adhesive force of the protective film-forming film 13 to the adherend (semiconductor wafer 8 ′) becomes higher. Moreover, the film 13 for protective film formation can be more easily cut | disconnected in the expanding process mentioned later because the thickness of the film 13 for protective film formation is below the said upper limit.
Here, the “thickness of the protective film-forming film 13” means the thickness of the entire protective film-forming film 13. For example, the thickness of the protective film-forming film 13 composed of a plurality of layers refers to the protective film. It means the total thickness of all layers constituting the forming film 13.

  The protective film-forming film 13 can be formed using a protective film-forming composition, which will be described later, containing the constituent materials.

In the laminated structure forming step, for example, using the 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 thickness direction in this order, 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 applied to the semiconductor wafer 8 ′. The adhesive layer 12 of the support sheet 10 is affixed to a surface (exposed surface, back surface) 13b opposite to the affixing surface (the one surface) 13a to constitute the composite sheet 1 for forming a protective film. The laminated structure 101 can be formed.
All of these are methods in which 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 ′.

On the other hand, in the laminated structure forming step, for example, the protective film-forming composite sheet 1 is used, and 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 ′, the laminated structure 101 can be formed.
Further, for example, after the protective film forming film 13 is attached to the back surface 8 b ′ of the semiconductor wafer 8 ′, the adhesive layer 12 of the support sheet 10 is attached to the back surface 13 b of the protective film forming film 13. After forming the forming composite sheet 1, the laminated structure 101 can also be formed by forming the modified layer 81 ′ inside the semiconductor wafer 8 ′.
In any of these methods, the modified layer 81 ′ is formed inside the semiconductor wafer 8 ′ after the protective film-forming composite sheet 1 is adhered to the semiconductor wafer 8 ′.

Among these, in the manufacturing method 1, the modified layer 81 ′ is formed inside the semiconductor wafer 8 ′ in the laminated structure forming step, and then the protective film-forming composite sheet 1 is attached to the semiconductor wafer 8 ′. It is preferable to be in a state of being made. This is because, as will be described later, the formation of the modified layer 81 ′ requires laser light irradiation. In order to form the modified layer 81 ′ by providing the semiconductor wafer 8 ′ in which the modified layer 81 ′ has been previously formed on the protective film forming film 13 and the support sheet 10 as described above, the support sheet 10 In addition, it is not necessary to transmit the protective film forming film 13 and irradiate the semiconductor wafer 8 'with laser light. Therefore, the support sheet 10 and the protective film-forming film 13 are not limited to those having laser beam transparency, and those having no laser beam transparency can be used, and the types of materials to be used are limited. Absent.
Further, in order to enhance the laser beam transmissivity, the outermost surface (back surface) 10b (in other words, the base material here) on the side opposite to the side on which the protective film forming film 13 of the support sheet 10 is provided. Since it is not necessary to improve the smoothness of the exposed surface 11 and the back surface 11b), blocking during the storage of the support sheet 10 can be suppressed.

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

Of 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 constituting the protective film forming composite sheet 1 is attached A back grind tape is preferably affixed to the circuit forming surface 8a ′. Even if the semiconductor wafer 8 ′ to which the back grind tape is attached is thin (even if the semiconductor wafer 8 ′ is a thin wafer), the protective film forming film 13 is applied. During handling, 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 will be described later.

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

  The back grind tape attached to the circuit forming surface 8a ′ of the semiconductor wafer 8 ′ is preferably removed (peeled) from the semiconductor wafer 8 ′ after the formation of the laminated structure 101 and before an expanding process described later. . After the formation of the laminated structure 101, damage to the semiconductor wafer 8 'is suppressed both when the back grind tape is removed and after it 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 be focused on a focal point set inside the semiconductor wafer 8 '.
That is, in the manufacturing method (1), before the laminated structure forming step, the semiconductor wafer 8 ′ before the protective film forming film 13 is further focused on the focal point set therein. Thus, it is preferable to have a modified layer forming step of forming a modified layer 81 ′ inside the semiconductor wafer 8 ′ by irradiating laser light.

The laser beam to be irradiated is preferably an infrared laser beam.
When the modified layer 81 ′ is formed, for example, in order to form the modified layer 81 ′ while minimizing damage to the surface of the semiconductor wafer 8 ′ or a region in the vicinity of the surface by irradiation with laser light, an 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 ′) on which the modified layer 81 ′ is to be formed is not particularly limited as long as the effects of the present invention are not impaired. It is preferable that it is 5-500 micrometers, and it is more preferable that it is 10-400 micrometers. When the thickness of the semiconductor wafer 8 ′ is equal to or greater than the lower limit value, the occurrence of breakage such as cracking or chipping of the semiconductor wafer 8 ′ is further suppressed. Further, since 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 process described later.

  The thickness of the semiconductor wafer 8 'can be adjusted by, for example, grinding the surface of the semiconductor wafer 8' opposite to the circuit forming surface 8a 'by a known method such as a method using a grinder. When the semiconductor wafer 8 ′ is thus ground, the back surface 8 b ′ 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 figure), and is shown in FIG. 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 the present specification, the protective film-forming film after cutting may be simply referred to as “protective film-forming film”.
The “direction of the surface 13 a of the protective film-forming film 13” has the same meaning as, for example, a direction parallel to one surface 11 a of the substrate 11 or one surface 12 a 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 adhesive layer 12 (in other words, the support sheet 10), and the protective film forming film 13 is cut. . At the same time, a force is applied to the semiconductor wafer 8 ′, so that 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, heating of the protective film-forming film 13 is not necessary in order to form the protective film after this step. Therefore, the support sheet 10 (for example, the base material 11) that does not have heat resistance and has a low elastic modulus can be used. Thus, 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 and cool the protective film forming film 13 while cooling the protective film forming film 13. By doing in this way, the protective film formation film 13 can be cut | disconnected easily.
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 (expanding 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 preferable that it is 1-60 mm / sec. When the expanding speed is within such a range, the effect of efficiently cutting the protective film-forming film 13 without any process abnormality is further enhanced. In particular, when the expanding speed is equal to or lower than the upper limit value, the semiconductor chip 8 is less likely to be damaged, and the occurrence of abnormality such as chipping at the cut portion of the protective film forming film 131 after cutting is further suppressed. .

○ Protective film formation process (protective film formation process (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 a protective film 131 ′, which is shown in FIG. Thus, the semiconductor chip 8 with the protective film (the semiconductor chip 8 having the 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, a laminated structure after processing in a state in which a plurality of semiconductor chips 8 with a protective film are provided on the support sheet 10 is denoted by reference numeral 101 ′. .

  In this step, heating is not necessary for forming the protective film 131 'in this way. Accordingly, a decrease in supportability (sagging) of the support sheet due to the shrinkage of the protective film 131 ′ is suppressed.

When the protective film forming film 131 is cured to form the protective film 131 ′, the irradiation condition (curing condition) of the energy rays is a degree of curing that the protective film 131 ′ exhibits its function sufficiently. It does not specifically limit as long as it is suitable, for example, according to the kind of film 131 for protective film formation.
For example, the illuminance of the energy rays when the protective film forming film 131 is cured is preferably ⁴ to 280 mW / cm ² . And it is preferable that the light quantity of an energy ray at the time of the said hardening is 3-1000 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 not impairing the effects of the present invention. It may be.

For example, FIG. 1 shows a support sheet in which a pressure-sensitive adhesive layer is provided on a substrate, but the support sheet is a substrate in which other layers than the pressure-sensitive adhesive layer are provided. May be.
In the present invention, the support sheet is preferably provided with a pressure-sensitive adhesive layer on a substrate, and more preferably provided with a pressure-sensitive adhesive layer in direct contact with the substrate.

Moreover, until now, as one embodiment of the manufacturing method (1), the laminated structure forming step, the expanding step (E1) and the protective film forming step (C1), and if necessary, the modified layer forming step. Although the manufacturing method of the semiconductor chip with a protective film which it has was demonstrated, the manufacturing method (1) may have other processes other than these 3 processes or 4 processes in the range which does not impair the effect of this invention. .
The other steps can be arbitrarily selected according to the purpose and are not particularly limited.

  In the manufacturing method (1), when a stacked structure other than the stacked structure 101 is used, or when the manufacturing method (1) includes the other steps, in the above-described embodiment, such a stacked structure is used. By adding the process for forming and the above-mentioned other processes at appropriate timings, the method for manufacturing a semiconductor chip with a protective film according to another embodiment of the manufacturing method (1) can be obtained.

◎ Manufacturing method of semiconductor chip with protective film (Manufacturing method (2))
In the method for producing 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. And forming a laminated structure in which a modified layer is formed inside the semiconductor wafer, and forming a protective film by irradiating the protective film-forming film with energy rays. A protective film forming step; and expanding the laminated structure after forming the protective film in a surface direction of the protective film to cut the protective film and dividing the semiconductor wafer at the portion of the modified layer And an expanding step for obtaining a plurality of semiconductor chips with protective films.

In the production method (2) of the present invention, the order of performing the step of forming the protective film and the step of expanding the laminated structure is opposite to that in the case of the production method (1) described above. .
The production method (2) of the present invention has the same effects as the production method (1) described above.

  That is, according to the production method (2) of the present invention, since the protective film-forming film is energy ray curable, heating is not necessary for the formation of the protective film, and it does not have heat resistance as a support sheet. Can be used. Therefore, the support sheet can be easily expanded and the protective film can be sufficiently cut. In addition, since heating is not required for forming the protective film, a decrease in supportability (sagging) on the support sheet of the semiconductor wafer is suppressed.

  Further, according to the production 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, in order to form the modified layer, there is no need to transmit the support sheet and the protective film forming film and irradiate the semiconductor wafer with laser light. There is no limitation. In addition, in order to increase the laser beam transmissivity, the smoothness of the surface of the outermost layer (for example, the exposed surface of the base material) on the side opposite to the side on which the protective film forming film is provided is improved. Therefore, it is possible to suppress the occurrence of blocking during storage of the support sheet.

  Furthermore, the manufacturing method (2) of the present invention avoids the problem by scraping a part of the semiconductor wafer, such as blade dicing, by adopting a method of dividing the semiconductor wafer at the portion of the modified layer. This is advantageous.

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

○ Laminated structure forming step In the laminated structure forming step of the production 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 manufacturing method (1) described above.

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 adhered 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 constituting the protective film forming composite sheet 1 is attached. Of these, a back grind tape is preferably affixed to the circuit forming surface 8a ′. In this case, the back grind tape is preferably removed (peeled) from the semiconductor wafer 8 ′ after the formation of the laminated structure 101 and before performing an expanding process described later.
In addition, the laminated structure 101 is preferably fixed to a ring frame or the like in the support sheet 10 as in the case of a conventional dicing sheet or the like.
The description of the details of the laminated structure forming step in the manufacturing method (2) is 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 be focused on a focal point set inside the semiconductor wafer 8 '.
That is, in the manufacturing method (2), before the laminated structure forming step, the semiconductor wafer 8 ′ before the protective film forming film 13 is further focused on the focal point set therein. Thus, it is preferable to have a modified layer forming step of forming a modified layer 81 ′ inside the semiconductor wafer 8 ′ by irradiating laser light.
The modified layer forming step in the production method (2) is the same as the modified layer forming step in the above-described production method (1), and the description thereof is omitted.

○ Protective film formation process (protective film formation process (C2))
In the protective film forming step (protective film forming step (C2)), the protective film 132 is formed by irradiating the protective film forming film 13 with energy rays, as shown in FIG.
The protective film 132 is the same as the protective film 131 in the above manufacturing method (1) except that it is not cut.
Moreover, this process is a protective film formation process (1) in the manufacturing method (1) described above except that an uncut protective film forming film is used instead of the cut protective film forming film as an object to be cured. The protective film formation step (C1)) can be performed by the same method. More specifically, it is as follows.

When the protective film-forming film 13 is cured and the protective film 132 is formed, the irradiation conditions (curing conditions) of the energy rays are particularly limited as long as the degree of curing is such that the protective film 132 sufficiently exhibits its function. It is not limited, For example, what is necessary is just to select suitably according to the kind of film 13 for protective film formation.
For example, the illuminance of the energy rays when the protective film-forming film 13 is cured is preferably ⁴ to 280 mW / cm ² . And it is preferable that the light quantity of an energy ray at the time of the said hardening is 3-1000 mJ / cm < ² >.
In this step, heating is not necessary for forming the protective film 132 as described above.

  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.3 (b), the laminated structure after such a film for protective film formation hardened | cured (it formed the protective film) is shown with the code | symbol 102. In FIG.

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

The “direction of the surface 132a of the protective film 132” has the same meaning as, for example, a direction parallel to the one surface 11a of the substrate 11 or the one surface 12a of the pressure-sensitive adhesive layer 12.
By this step, a plurality of target semiconductor chips 8 with a protective film (semiconductor chips 8 having a protective film 132 ′ on the back surface 8b) can be obtained at once. In FIG.3 (c), the laminated structure after a process of the state provided with the some semiconductor chip 8 with a protective film on such a support sheet 10 is shown with code | symbol 102 '. .

  In this manufacturing method (1), except that a laminated structure that is an object of expansion is replaced with a protective film-forming film instead of a protective film that is a cured product thereof, this step is used. It can be performed by the same method 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, a force is applied to the semiconductor wafer 8 ′, so that 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, heating of the protective film-forming film 13 is unnecessary in order to form the protective film before this step. Therefore, the support sheet 10 (for example, the base material 11) that does not have heat resistance and has a low elastic modulus can be used. Thus, 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 position.

In the expanding step, the laminated structure 102 can be expanded and the protective film 132 can be cut while cooling the protective film 132. By doing so, the protective film 132 can be easily cut.
Although the cooling temperature of the protective film 132 at the time of expansion is not specifically limited, It is preferable that it is -15-10 degreeC from the point which can cut | disconnect the protective film 132 more easily.
Unlike the case of the manufacturing method (1), the protective film 132 may be expanded at room temperature or while heating without being cooled in some cases.

  The expansion 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 it is more preferable that it is 1-60 mm / sec. When the expanding speed is within such a range, the effect of efficiently cutting the protective film 132 without any process abnormality becomes higher. In particular, when the expanding speed is equal to or lower than the upper limit value, the semiconductor chip 8 is less likely to be damaged, and the occurrence of abnormality such as chipping in the cut portion 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. 1C, and the laminated structure 102 ′ after processing is processed as shown in FIG. 1C. This is substantially the same as the subsequent laminated structure 101 ′.

  As in the case of the manufacturing method (1), in the manufacturing method (2), the laminated structure is not limited to the one shown here. The configuration of the part may be changed, deleted, or added.

For example, FIG. 3 shows a support sheet in which a pressure-sensitive adhesive layer is provided on the base material, but the support sheet is a base material in which another layer other than the pressure-sensitive adhesive layer is provided. May be.
In the present invention, the support sheet is preferably provided with a pressure-sensitive adhesive layer on a substrate, and more preferably provided with a pressure-sensitive adhesive layer in direct contact with the substrate.

Moreover, until now, as one embodiment of the manufacturing method (2), the laminated structure forming step, the protective film forming step (C2) and the expanding step (E2), and, if necessary, the modified layer forming step. Although the manufacturing method of the semiconductor chip with a protective film which it has was demonstrated, the manufacturing method (2) may have other processes other than these 3 processes or 4 processes in the range which does not impair the effect of this invention. .
The other steps can be arbitrarily selected according to the purpose and are not particularly limited.

  In the production method (2), when a laminated structure other than the laminated structure 102 is used, or when the production method (2) includes the other steps, such a laminated structure is used in the above-described embodiment. By adding the process for forming and the above-mentioned other processes at appropriate timings, the method for manufacturing a semiconductor chip with a protective film according to another embodiment of 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 is reversed. Which production method is selected is arbitrary and may be selected according to the purpose. Usually, since the protective film-forming film has a higher adhesive force to the adherend than the protective film, the production method (1) for expanding the laminated structure provided with the protective film-forming film is a semiconductor chip. The effect of suppressing scattering (so-called chip jump) is high.

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

◇ Base material The base material is in the form of a sheet or film, and examples of the constituent material 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 polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin. Polyolefin; Ethylene-based copolymer such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-norbornene copolymer (ethylene as a monomer) A copolymer obtained by using a vinyl chloride resin such as polyvinyl chloride and vinyl chloride copolymer (a resin obtained by using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene Naphtha Polyesters such as polyesters, polybutylene terephthalates, polyethylene isophthalates, polyethylene-2,6-naphthalene dicarboxylates, wholly aromatic polyesters in which all the structural units have aromatic cyclic groups; Poly (meth) acrylic acid ester; Polyurethane; Polyurethane acrylate; Polyimide; Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified polyphenylene oxide; Polyphenylene sulfide; Polysulfone;
Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and other resin, are mentioned, for example. The polymer alloy of the polyester and the other resin is preferably one in which the amount of the resin other than the polyester is relatively small.
Examples of the resin include a crosslinked resin in which one or more of the resins exemplified so far are crosslinked; modification of an ionomer or the like using one or more of the resins exemplified so far. Resins can also be mentioned.

  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 substrate may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

  The substrate preferably has a high thickness accuracy, that is, a substrate in which variation in thickness is suppressed regardless of the part. Among the above-described constituent materials, examples of materials that can be used to construct such a substrate with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymers, and the like. Is mentioned.

  The base material contains various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin. May be.

◇ Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer is in the form of a sheet or a film and contains a pressure-sensitive adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferable. .

  In the present invention, the “adhesive resin” is a concept including both an adhesive resin and an adhesive resin. For example, the resin itself has an adhesive property, Also included are resins that exhibit tackiness when used in combination with other components such as additives, and resins that exhibit adhesiveness due to the presence of a trigger such as heat or water.

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

<< Adhesive composition >>
The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, an adhesive layer can be formed in the target site | part by applying an adhesive composition to the formation object surface of an adhesive layer, and making it dry as needed. A more specific method for forming the pressure-sensitive adhesive layer will be described later in detail, along with methods for forming other layers. The ratio of the content of components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the content of the components of the pressure-sensitive adhesive layer. In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and includes a temperature of 15 to 25 ° C., for example.

  The adhesive composition may be applied by a known method, for example, an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater. And 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 the pressure-sensitive adhesive composition is preferably heat-dried when it contains a solvent described later, and in this case, for example, at 70 to 130 ° C. for 10 seconds to It is preferable to dry under conditions 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, non-energy ray-curable pressure-sensitive adhesive A pressure-sensitive adhesive composition (I-1) containing a resin (I-1a) (hereinafter sometimes abbreviated as “adhesive resin (I-1a)”) and an energy ray-curable compound; Energy-ray-curable adhesive resin (I-2a) (hereinafter referred to as “adhesive resin (I-2a)”) in which an unsaturated group is introduced into the side chain of the linear-curable adhesive resin (I-1a) Pressure-sensitive adhesive composition (I-2) containing the adhesive resin (I-2a) and an energy ray-curable compound (I-3), etc. Is 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.
As said acrylic resin, the acrylic polymer which has a structural unit derived from the (meth) acrylic-acid alkylester at least is mentioned, for example.
The acrylic resin may have only one type of structural unit, two or more types, and in the case of 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 preferred.
More specifically, as (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (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, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid n-octyl, (meth) acrylic acid n-nonyl, (meth) acrylic acid isononyl, (meth) acrylic acid decyl, (meta ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) Decyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples thereof include octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecyl (meth) acrylate, icosyl (meth) acrylate, and the like.

  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 in which the alkyl group has 4 or more carbon atoms. And from the point which the adhesive force of an adhesive layer improves more, it is preferable that carbon number of the said alkyl group is 4-12, and it is more preferable that it is 4-8. In addition, 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 an alkyl (meth) acrylate.
As the functional group-containing monomer, for example, the functional group reacts with a cross-linking agent described later to become a starting point of cross-linking, or the functional group reacts with an unsaturated group in the unsaturated group-containing compound described later. And those that allow 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, and an epoxy group.
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, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic polymers such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.

  Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Examples include ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; and (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate. It is done.

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

  As for the functional group-containing monomer constituting the acrylic polymer, only one type may be used, or two or more types may be used, 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 and more preferably 2 to 32% by mass with respect to the total amount of the structural unit. 3 to 30% by mass is particularly preferable.

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 acrylic polymer may further have a structural unit derived from another monomer.
The other monomer is not particularly limited as long as it is copolymerizable with (meth) acrylic acid alkyl ester or the like.
Examples of the other monomer include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

  The other monomer constituting the acrylic polymer may be only one type, or two or more types, and when there are two or more types, 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, the functional group in the acrylic polymer is reacted with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (energy ray-polymerizable group). It can be used as the resin (I-2a).

  Only 1 type may be sufficient as the adhesive resin (I-1a) which an adhesive composition (I-1) contains, and when it is 2 or more types, those combinations and ratios are arbitrary. You can choose.

  In the pressure-sensitive adhesive composition (I-1), the ratio of the content of the pressure-sensitive resin (I-1a) to the total content of components other than the solvent (that is, the pressure-sensitive adhesive layer (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 that have an energy ray-polymerizable unsaturated group and can be cured by irradiation with energy rays.
Among the energy ray curable compounds, examples of the monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,4. Polyhydric (meth) acrylates such as butylene glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; polyether (meth) acrylate; epoxy ( And (meth) acrylate.
Among the energy ray-curable compounds, examples of the oligomer include an oligomer formed by polymerizing the monomers exemplified above.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer from the viewpoint that the molecular weight is relatively large and the storage elastic modulus of the pressure-sensitive adhesive layer is hardly lowered.

  The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio 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. % Is particularly preferred.

[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 (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), a pressure-sensitive adhesive composition ( I-1) preferably further contains a crosslinking agent.

The said crosslinking agent reacts with the said functional group, for example, and bridge | crosslinks adhesive resin (I-1a).
As a crosslinking agent, for example, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isocyanate-based cross-linking agents such as adducts of these diisocyanates (cross-linking agents having an isocyanate group); epoxy-based cross-linking agents such as ethylene glycol glycidyl ether ( A cross-linking agent having a glycidyl group); an aziridine-based cross-linking agent such as hexa [1- (2-methyl) -aziridinyl] triphosphatriazine (a cross-linking agent having an aziridinyl group); a metal chelate cross-linking agent such as an aluminum chelate (metal) Cross-linking agent having a chelate structure); isocyanurate-based cross-linking agent (cross-linking agent having an isocyanuric acid skeleton) and the like.
From the viewpoint of improving the cohesive strength of the pressure-sensitive adhesive and reducing the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer, and being easily available, the cross-linking agent is preferably an isocyanate-based cross-linking agent.

  Only 1 type may be sufficient as the crosslinking agent which adhesive composition (I-1) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  In the said adhesive composition (I-1), it is preferable that content of a crosslinking agent is 0.01-50 mass parts with respect to 100 mass parts of content of adhesive resin (I-1a), More preferably, it is 0.1-20 mass parts, and it is especially preferable that it is 0.3-15 mass parts.

[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 energy rays of relatively low energy 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, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy -2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2 Acetophenone 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-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene Titanocene compound; thioxanthone compound such as thioxanthone; peroxide compound; diketone compound 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.
As the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

  Only 1 type may be sufficient as the photoinitiator which adhesive composition (I-1) contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

  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 energy beam curable compound. The amount is 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-1) may contain other additives that do not fall under any of the above-described components within a range that does not impair the effects of the present invention.
Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. And known additives such as reaction retarders and crosslinking accelerators (catalysts).
The reaction retarder is, for example, an undesired cross-linking reaction in the preserving adhesive composition (I-1) by the action of the catalyst mixed in the adhesive composition (I-1). It suppresses progress. Examples of the reaction retarder include those that form a chelate complex by chelation against a catalyst, and more specifically, those having two or more carbonyl groups (—C (═O) —) in one molecule. Can be mentioned.

  As for the other additive which an adhesive composition (I-1) contains, only 1 type may be sufficient and it may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

[solvent]
The pressure-sensitive adhesive composition (I-1) may contain a solvent. The pressure-sensitive adhesive composition (I-1) contains a solvent, thereby improving the suitability for application to the surface to be coated.

  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 and n-hexane and the like. Aliphatic hydrocarbons; aromatic hydrocarbons such as toluene and xylene; and alcohols such as 1-propanol and 2-propanol.

  As said solvent, you may use as it is in adhesive composition (I-1) as it is, for example, without removing what was used at the time of manufacture of adhesive resin (I-1a) from adhesive resin (I-1a). And the same or different kind of solvent used at the time of manufacture of adhesive resin (I-1a) may be added separately at the time of manufacture of adhesive composition (I-1).

  Only 1 type may be sufficient as the solvent which an adhesive composition (I-1) contains, and when 2 or more types may be sufficient, those combinations and ratios can be selected arbitrarily.

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

<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 an unsaturated group-containing compound having an energy ray polymerizable unsaturated group with a functional group in the adhesive resin (I-1a).

The unsaturated group-containing compound can be bonded to the adhesive resin (I-1a) by further reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray polymerizable unsaturated group. A compound having a group.
Examples of the energy ray polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (ethenyl group), an allyl group (2-propenyl group), and the like, and a (meth) acryloyl group is preferable.
Examples of the group capable of binding to the functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and a glycidyl group capable of binding to a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of binding to a carboxy group or an epoxy group. Etc.

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

  The pressure-sensitive adhesive composition (I-2) contained in the pressure-sensitive adhesive composition (I-2a) may be only one type, or 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 resin (I-2a) to the total content of components other than the solvent (that is, the pressure-sensitive adhesive layer (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, an adhesive composition ( I-2) may further contain a crosslinking agent.

As said crosslinking agent in adhesive composition (I-2), the same thing as the crosslinking agent in adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the crosslinking agent which adhesive composition (I-2) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  In the said adhesive composition (I-2), it is preferable that content of a crosslinking agent is 0.01-50 mass parts with respect to 100 mass parts of content of adhesive resin (I-2a), More preferably, it is 0.1-20 mass parts, and it is especially preferable that it is 0.3-15 mass parts.

[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 energy rays of relatively low energy such as ultraviolet rays.

As said photoinitiator in an adhesive composition (I-2), the same thing as the photoinitiator in an adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the photoinitiator which adhesive composition (I-2) contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

  In the 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 adhesive resin (I-2a). 0.03 to 10 parts by mass is more preferable, and 0.05 to 5 parts by mass is particularly preferable.

[Other additives]
The pressure-sensitive adhesive composition (I-2) may contain other additives that do not correspond to any of the above-described components within a range not impairing the effects of the present invention.
As said other additive in an adhesive composition (I-2), the same thing as the other additive in an adhesive composition (I-1) is mentioned.
As for the other additive which an adhesive composition (I-2) contains, only 1 type may be sufficient and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

[solvent]
The pressure-sensitive adhesive composition (I-2) may contain a solvent for the same purpose as that 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).
Only 1 type may be sufficient as the solvent which an adhesive composition (I-2) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
In the pressure-sensitive adhesive composition (I-2), the content of the solvent is not particularly limited, and may be adjusted as appropriate.

<Adhesive composition (I-3)>
As described above, the pressure-sensitive adhesive composition (I-3) contains the pressure-sensitive adhesive 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 resin (I-2a) to the total content of components other than the solvent (that is, the pressure-sensitive adhesive layer (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 that have an energy ray-polymerizable unsaturated group and can be cured by irradiation with energy rays. The same thing as the energy-beam curable compound which a thing (I-1) contains is mentioned.
The energy ray-curable compound contained in the pressure-sensitive adhesive composition (I-3) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected. .

  In the said adhesive composition (I-3), content of the said energy-beam curable compound is 0.01-300 mass parts with respect to 100 mass parts of adhesive resin (I-2a) content. It is preferable that it is 0.03-200 mass parts, and it is especially preferable that it is 0.05-100 mass parts.

[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 energy rays of relatively low energy such as ultraviolet rays.

As said photoinitiator in an adhesive composition (I-3), the same thing as the photoinitiator in an adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the photoinitiator which an adhesive composition (I-3) contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

  In the 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 adhesive resin (I-2a) and the energy ray curable compound. It 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-described components within a range that does not impair the effects of the present invention.
As said other additive, the same thing as the other additive in adhesive composition (I-1) is mentioned.
As for the other additive which an adhesive composition (I-3) contains, 1 type may be sufficient, and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

[solvent]
The pressure-sensitive adhesive composition (I-3) may contain a solvent for the same purpose as that 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).
Only 1 type may be sufficient as the solvent which an adhesive composition (I-3) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
In the pressure-sensitive adhesive composition (I-3), the content of the solvent is not particularly limited, and may be adjusted as appropriate.

<Adhesive composition other than the 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. General pressure-sensitive adhesive composition other than these three types of pressure-sensitive adhesive compositions (referred to herein as “pressure-sensitive adhesive compositions other than pressure-sensitive adhesive compositions (I-1) to (I-3)”) But it can be used similarly.

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.
Non-energy ray curable pressure-sensitive adhesive compositions include, for example, acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. Pressure-sensitive adhesive resin (I-1a) -containing pressure-sensitive adhesive composition (I-4), and those containing an acrylic resin are preferred.

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

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

[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-4) include the same ones as the pressure-sensitive adhesive resin (I-1a) in the pressure-sensitive adhesive composition (I-1).
The pressure-sensitive adhesive composition (I-1a) contained in the pressure-sensitive adhesive composition (I-4) may be only one type, or 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 resin (I-1a) to the total content of components other than the solvent (that is, the pressure-sensitive adhesive layer (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 (meth) acrylic acid alkyl ester is used as the adhesive resin (I-1a), a pressure-sensitive adhesive composition ( I-4) preferably further contains a crosslinking agent.

As a crosslinking agent in adhesive composition (I-4), the same thing as the crosslinking agent in adhesive composition (I-1) is mentioned.
Only 1 type may be sufficient as the crosslinking agent which adhesive composition (I-4) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

  In the said adhesive composition (I-4), it is preferable that content of a crosslinking agent is 0.01-50 mass parts with respect to 100 mass parts of content of adhesive resin (I-1a), More preferably, it is 0.1-20 mass parts, and it is especially preferable that it is 0.3-15 mass parts.

[Other additives]
The pressure-sensitive adhesive composition (I-4) may contain other additives that do not fall under any of the above-described components within a range that does not impair the effects of the present invention.
As said other additive, the same thing as the other additive in adhesive composition (I-1) is mentioned.
As for the other additive which an adhesive composition (I-4) contains, only 1 type may be sufficient and 2 or more types may be sufficient, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

[solvent]
The pressure-sensitive adhesive composition (I-4) may contain a solvent for the same purpose as that 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).
Only 1 type may be sufficient as the solvent which adhesive composition (I-4) contains, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
In the pressure-sensitive adhesive composition (I-4), the content of the solvent is not particularly limited, and may be adjusted as appropriate.

<< Method for producing pressure-sensitive adhesive composition >>
The pressure-sensitive adhesive compositions other than the pressure-sensitive adhesive compositions (I-1) to (I-3) such as the pressure-sensitive adhesive compositions (I-1) to (I-3) and the pressure-sensitive adhesive composition (I-4) It is obtained by blending each component for constituting the pressure-sensitive adhesive composition, such as the pressure-sensitive adhesive and components other than the pressure-sensitive adhesive, if necessary.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, 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 form a protective film. This protective film is for protecting the back surface (surface opposite to the circuit forming surface) of the semiconductor wafer or semiconductor chip. The protective film-forming film is soft and can be easily attached to an 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 a thermosetting protective film-forming film.
By providing the protective film-forming film on the support sheet, a protective film-forming composite sheet can be configured.

  In the present specification, the “protective film-forming film” means a film before curing, and the “protective film” means a film obtained by curing the protective film-forming 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 tacky, and more preferably uncured and tacky.

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

  For example, when the protective film-forming film has a release film on both sides, the coating surface of the protective film-forming composition is the surface of any one of these release films (preferably the release-treated surface). It can be. On the other hand, when the protective film-forming film is provided on the support sheet, the coating surface of the protective film-forming composition can be the surface of the support sheet.

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

  Coating of the composition for forming a protective film may be performed by a known method, for example, air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, curtain coater, die coater, knife coater, Examples include a method using various coaters such as a screen coater, a Meyer bar coater, and a kiss coater.

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

<Composition for forming protective film (IV-1)>
Examples of the protective film forming composition include a 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 beam curable component (a) include a polymer (a1) having an energy beam curable group and a weight average molecular weight of 80000 to 2000000, and an energy beam curable group having a molecular weight of 100 to 80000. A compound (a2) is mentioned. The polymer (a1) may be at least partially 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 2,000,000)
Examples of the polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound, An acrylic resin (a1-1) formed 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 possessed by 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 a hydrogen atom) Group), an epoxy group, and the like. However, the functional group is preferably a group other than a carboxy group from the viewpoint of preventing corrosion of a circuit such as a semiconductor wafer or a semiconductor chip.
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 an acrylic monomer having the functional group and an acrylic monomer having no functional group. In addition to monomers, monomers other than acrylic monomers (non-acrylic monomers) may be copolymerized.
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, (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic polymers such as vinyl alcohol and allyl alcohol Saturated alcohol (unsaturated alcohol which does not have a (meth) acryloyl skeleton) etc. are mentioned.

  Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citracone Examples include ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the ethylenically unsaturated dicarboxylic acids; and (meth) acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate. It is done.

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

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

  Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate 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 (meth) acrylate), (meth ) Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, ( Examples include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester, such as octadecyl (meth) acrylate (stearyl (meth) acrylate), has a chain structure having 1 to 18 carbon atoms.

  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 aryl ester such as (meth) acrylic acid phenyl ester, etc .; (meth) acrylic acid ester having an aromatic group; non-crosslinkable (meth) acrylamide and Derivatives thereof: (meth) acrylic acid esters having a non-crosslinking tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate are also included. .

  The acrylic monomer which does not have the functional group constituting the acrylic polymer (a11) may be only one type, or 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; styrene.
The said non-acrylic monomer which comprises the said acrylic polymer (a11) may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

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

  1 type may be sufficient as the said acrylic polymer (a11) which comprises the said acrylic resin (a1-1), and when it is 2 or more types and they are 2 or more types, those combinations and ratios are 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. It is especially preferable that it is -20 mass%.

Energy beam 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 preferred, and those having an isocyanate group as the group are more preferred. For example, when the energy beam curable compound (a12) has an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

  The energy beam curable compound (a12) preferably has 1 to 5 energy beam curable groups in one molecule, and more preferably has 1 to 3 energy beam curable groups.

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

  The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type, or 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) with respect to the content of the functional group derived from the acrylic polymer (a11). The ratio 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 within such a range, the adhesive force of the protective film formed by curing is further increased. In addition, when the energy ray curable compound (a12) is a monofunctional compound (having one of the groups per 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 polymer (a1) has a weight average molecular weight (Mw) of preferably 100,000 to 2,000,000, and more preferably 300,000 to 1500,000.

  In the case where the polymer (a1) is at least partly crosslinked by the crosslinking agent (f), the polymer (a1) is described as constituting the acrylic polymer (a11). A monomer that does not correspond to any of the above-described monomers and has a group that reacts with the crosslinking agent (f) is polymerized to be crosslinked at the group that reacts with the crosslinking agent (f). And in the group which reacts with the said functional group derived from the said energy-beam curable compound (a12), what was bridge | crosslinked may be used.

  The polymer (a1) 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 two or more types. Combinations and ratios can be arbitrarily selected.

(Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80,000)
The energy ray curable group having an energy ray curable group and having a molecular weight of 100 to 80,000 (a2) includes a group containing an energy ray curable double bond, and (meth) is preferable. An acryloyl group, a vinyl group, etc. are mentioned.

  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. A phenol resin etc. are mentioned.

Among the compounds (a2), examples of the low molecular weight compound having an energy ray curable group include polyfunctional monomers or oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylate 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 -((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane, tricyclodecane dimethanol di (meth) acrylate (tri Cyclodecane dimethylol di (meth) ac Relate), 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2 , 2-bis [4-((meth) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy Difunctional (meth) acrylates such as 1,3-di (meth) acryloxy propane;
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 (meth) acrylate;
Examples include polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

  Among the compounds (a2), the epoxy resin having an energy ray curable group and the phenol resin having an energy ray curable group are described in, for example, paragraph 0043 of “JP 2013-194102 A”. Things can be used. Such a resin 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.

  1 type may be sufficient as the said compound (a2) which the composition for protective film formation (IV-1) and the film for protective film formation contain, 2 or more types, and when they are 2 or more types, those combination The ratio can be arbitrarily selected.

[Polymer (b) having no energy ray curable group]
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 have an energy ray-curable group. It is also preferable to contain (b).
The polymer (b) may be at least partially crosslinked by the 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 thereof include resins.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as “acrylic polymer (b-1)”).

  The acrylic polymer (b-1) may be a known one, for example, a homopolymer of one acrylic monomer, or a copolymer of two or more acrylic monomers. Alternatively, it may be a copolymer of one or two or more acrylic monomers and a monomer (non-acrylic monomer) other than one or two or more 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, glycidyl group-containing (meth) acrylic acid ester, Examples include hydroxyl group-containing (meth) acrylic acid esters and substituted amino group-containing (meth) acrylic acid esters. Here, the “substituted amino group” is as described above.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (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, (meth ) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic Undecyl acid, dodecyl (meth) acrylate (lauryl (meth) acrylate), (meth ) Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, ( Examples include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester, such as octadecyl (meth) acrylate (stearyl (meth) acrylate), has a chain structure having 1 to 18 carbon atoms.

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

Examples of the glycidyl group-containing (meth) acrylic ester include glycidyl (meth) acrylate.
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 include propyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
Examples of the substituted amino group-containing (meth) acrylic acid ester include N-methylaminoethyl (meth) acrylate.

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

As the polymer (b) at least partially crosslinked by the crosslinking agent (f) and not having the energy ray curable group, for example, the reactive functional group in the polymer (b) is a crosslinking agent (f ).
The reactive functional group may be appropriately selected according to the type of the crosslinking agent (f) and the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group. Among these, a hydroxyl group having high reactivity with an isocyanate group. Is preferred. Further, when the crosslinking agent (f) is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, etc. Among them, a carboxy group having high reactivity with an epoxy group. Groups are preferred. However, the reactive functional group is preferably a group other than a carboxy group in terms of preventing corrosion of a circuit of a semiconductor wafer or a semiconductor chip.

  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), those having the reactive functional group as one or both of the acrylic monomer and the non-acrylic monomer mentioned as monomers constituting the polymer. Use it. 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. Examples of the acrylic monomer or non-acrylic monomer include those obtained by polymerizing a monomer in which one or two or more hydrogen atoms are substituted with the reactive functional group.

  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 unit constituting the polymer is 1-25. It is preferable that it is mass%, and it is more preferable that it is 2-20 mass%. When the ratio is within such a range, the degree of cross-linking becomes a more preferable range in the polymer (b).

  The weight average molecular weight (Mw) of the polymer (b) having no energy ray curable group is 10,000 to 2,000,000 from the point that the film-forming property of the protective film-forming composition (IV-1) becomes better. It is preferable and it is more preferable that it is 100,000-1500,000.

  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 more than species, their combination and ratio can be arbitrarily selected.

  Examples of the protective film-forming composition (IV-1) include those containing either one or both of the polymer (a1) and the compound (a2). And when the composition (IV-1) for protective film formation contains the said compound (a2), it is preferable to also contain the polymer (b) which does not have an energy-beam curable group further, in this case, It is also preferable to contain (a1). Moreover, the composition (IV-1) for forming a protective film does not contain the compound (a2), and contains both the polymer (a1) and the polymer (b) having no energy ray curable group. It 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 beam curable group. The amount is preferably 400 parts by mass, and more preferably 30 to 350 parts by mass.

  In the protective film-forming composition (IV-1), the total content of the energy beam curable component (a) and the polymer (b) having no energy beam curable group with respect to the total content of 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 is 5 to 90% by mass. Preferably, it is 10-80 mass%, It is more preferable that it is 15-70 mass%. When the ratio of the total content is within 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) ) And the protective film-forming film, the content of the polymer (b) is preferably 3 to 160 parts by mass with respect to 100 parts by mass of the energy ray-curable component (a). More preferably, it is -130 mass parts. 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), crosslinking agent (f), colorant (g), thermosetting component (h), curing accelerator (i), and general-purpose additive (z). You may contain 1 type, or 2 or more types 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 by heating. Adhesive strength to the adherend is improved, and the strength of the protective film formed from this protective film-forming film is also improved.

[Photoinitiator (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, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone, 2 Acetophenone compounds such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide Compound; α-ketol compound such as 1-hydroxycyclohexyl phenyl ketone; azo compound such as azobisisobutyronitrile; titanocene compound such as titanocene; thioxanthone compound such as thioxanthone; benzophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime Benzophenone compounds such as); diketone compounds such as diacetyl; benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methyl) Vinyl) phenyl] propanone; 2-chloroanthraquino Or the like.
As the photopolymerization initiator (c), for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can be used.

  1 type may be sufficient as the photoinitiator (c) which the composition for protective film formation (IV-1) contains, and when it is 2 or more types, those combinations and ratios are arbitrary. Can be selected.

  In the case where the photopolymerization initiator (c) is used, in the protective film-forming composition (IV-1), the content of the photopolymerization initiator (c) is 100 parts by mass of the energy ray curable compound (a). 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)]
When the protective film-forming film contains the filler (d), the protective film obtained by curing the protective film-forming film can easily adjust the thermal expansion coefficient. By optimizing the object to be formed, the reliability of the package obtained using this protective film is further improved. Moreover, the moisture absorption rate of a protective film can be reduced or heat dissipation can be improved because the film for protective film formation contains a filler (d).
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, bengara, silicon carbide, boron nitride, and the like; beads formed by spheroidizing these inorganic fillers; surface modification of these inorganic fillers Products; 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 diameter 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 diameter 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 adhesion to the object to be formed of the protective film.
In the present specification, “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 of two or more types. The ratio can be arbitrarily selected.

  In the case of using the filler (d), in the protective film forming composition (IV-1), the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, for forming the protective film) The film filler (d) content) is preferably 5 to 83% by mass, and more preferably 7 to 78% by mass. When the content of the filler (d) is in such a range, the adjustment of the thermal expansion coefficient becomes easier.

[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 adhesion 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 the heat resistance.

The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the energy beam curable component (a), the polymer (b) having no energy beam curable group, and the like. More preferably, it is a silane coupling agent.
Preferred examples of the silane coupling agent include 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-mercaptopropi Examples include trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. It is done.

  The coupling agent (e) 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 two or more types. Combinations and ratios can be arbitrarily selected.

  When the coupling agent (e) is used, in the protective film-forming composition (IV-1) and the protective film-forming film, the content of the coupling agent (e) 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, It is especially preferable that it is 0.1-5 mass parts. When the content of the coupling agent (e) is equal to or higher than the lower limit, the dispersibility of the filler (d) in the resin is improved and the adhesion of the protective film-forming film to the adherend is improved. The effect by using a coupling agent (e) etc. is acquired more notably. Moreover, generation | occurrence | production of an outgas is suppressed more because the said content of a coupling agent (e) is below the said upper limit.

[Crosslinking agent (f)]
By using the crosslinking agent (f) and crosslinking the polymer (b) having no energy beam curable component (a) or energy beam curable group, the initial adhesive force and cohesive force of the protective film-forming film. Can be adjusted.

  Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like. Is 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”). A trimer such as the aromatic polyisocyanate compound, isocyanurate and adduct; a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyvalent isocyanate compound and the polyol compound. Etc. The “adduct body” includes the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound, or the alicyclic polyvalent isocyanate compound, and a low amount of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, or the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include an xylylene diisocyanate adduct of trimethylolpropane as described later. The “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and an isocyanate group at the end 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 Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylol Any one of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate is added to all or some hydroxyl groups of a polyol such as propane. Like lysine diisocyanate and the like; the compound or two or more are added.

  Examples of the organic polyvalent imine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, and tetramethylolmethane. -Tri-β-aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.

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

  The composition for forming a protective film (IV-1) and the crosslinking agent (f) contained in the film for forming a protective film may be only one kind, two kinds or more, and combinations of two or more kinds. The ratio can be arbitrarily selected.

  In the case where the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the protective film-forming composition (IV-1) is such that the energy ray curable component (a) and the energy ray curable group are not included. The total content of the combined (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 preferred. When the content of the cross-linking agent (f) is equal to or higher than the lower limit value, the effect of using the cross-linking agent (f) is more remarkably obtained. Moreover, the excessive use of a crosslinking agent (f) is suppressed because the said content of a crosslinking agent (f) is below the said upper limit.

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

  Examples of the organic pigments and organic dyes include aminium dyes, cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanines. Dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes , Pyrrole dyes, thioindigo dyes, metal complex dyes (metal complex dyes), dithiol metal complex dyes, indolephenol dyes, triallylmethane dyes, anthraquinone dyes, dioxazine dyes, naphthol dyes, azomethine dyes Pigment Benzimidazolone dyes, pyranthrone pigments and threne color like.

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

  Only 1 type may be sufficient as the coloring agent (g) which the composition for protective film formation (IV-1) and the film for protective film formation contain, and when it is 2 or more types, they are combinations. The ratio can be arbitrarily selected.

  In the case of using the colorant (g), the content of the colorant (g) in the protective film-forming film may be appropriately adjusted according to the purpose. For example, when the print visibility is adjusted by adjusting the content of the colorant (g) and adjusting 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 components (that is, the content of the colorant (g) in 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. The effect by using a colorant (g) is acquired more notably because the content of the colorant (g) is not less than the lower limit. Moreover, the excessive use of a coloring agent (g) is suppressed because the said content of a coloring agent (g) is below the said upper limit.

[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 type, two or more types, and when two or more types, These combinations and ratios can be arbitrarily selected.

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

(Epoxy thermosetting resin)
The epoxy thermosetting resin includes an epoxy resin (h1) and a thermosetting agent (h2).
The epoxy thermosetting resin contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, two or more types, and when two or more types, Combinations and ratios can be arbitrarily selected.

・ Epoxy resin (h1)
Examples of the epoxy resin (h1) include known ones such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like, and bifunctional or higher functional epoxy compounds are listed.

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

Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds obtained by converting a part of the epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group directly couple | bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth) acryloyl group, (meth). An acrylamide group etc. are mentioned, An acryloyl group is preferable.

Although the number average molecular weight of an epoxy resin (h1) is not specifically limited, It is preferable that it is 300-30000 from the sclerosis | hardenability of the film for protective film formation, and the intensity | strength and heat resistance of a protective film, and is 400-10000. More preferably, it is particularly preferably 500 to 3000.
The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, and 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, their combination and ratio can be arbitrarily selected.

・ Thermosetting agent (h2)
The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).
As a thermosetting agent (h2), the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. 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 has been anhydrideized, and the like, and a phenolic hydroxyl group, an amino group, or an acid group has been anhydrideized. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (h2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.
Among the thermosetting agents (h2), examples of the amine-based curing agent having an amino group include dicyandiamide (hereinafter sometimes abbreviated as “DICY”).

The thermosetting agent (h2) may have an unsaturated hydrocarbon group.
As the thermosetting agent (h2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, an 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 an unsaturated hydrocarbon group described above.

  In the case where a phenolic curing agent is used as the thermosetting agent (h2), it is preferable that the thermosetting agent (h2) has a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet. .

Of the thermosetting agent (h2), for example, the number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolac-type phenol resin, a dicyclopentadiene-based phenol resin, an aralkyl phenol resin is preferably 300 to 30,000, More preferably, it is 400-10000, and it is especially preferable that it is 500-3000.
Of the thermosetting agent (h2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

  A thermosetting agent (h2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

  When the thermosetting component (h) is used, in the protective film-forming composition (IV-1) and the protective film-forming film, the content of the thermosetting agent (h2) is 100% of the epoxy resin (h1). It is preferable that it is 0.01-20 mass parts with respect to a 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 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 examples of the curing accelerator (i) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine, etc. Organic phosphines, tetraphenylphosphonium tetraphenylborate, tetraphenylboron salts such as triphenylphosphine tetraphenylborate and the like.

A hardening accelerator (i) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
When using hardening accelerator (i), content of the composition (IV-1) for protective film formation and the hardening accelerator (i) of the film for protective film formation is not specifically limited, According to the component to use together. What is necessary is just to select suitably.

[General-purpose additive (z)]
The general-purpose additive (z) may be a known one, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples include a plasticizer, an antistatic agent, an antioxidant, and a gettering agent. Is 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, Combinations and ratios can be arbitrarily selected.
When the general-purpose additive (z) is used, the content of the general-purpose additive (z) in the protective film-forming composition (IV-1) and the protective film-forming film is not particularly limited and is appropriately selected depending on the purpose. do it.

[solvent]
The protective film-forming composition (IV-1) preferably further contains a solvent. The protective film-forming composition (IV-1) containing a solvent has good handleability.
The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. An ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone; an ether such as tetrahydrofuran; an amide (a compound having an amide bond) such as dimethylformamide or N-methylpyrrolidone;
Only 1 type may be sufficient as the solvent which the composition for protective film formation (IV-1) contains, and when it is 2 or more types, when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

  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 more uniformly mixed. It is preferable.

<< Method for producing protective film-forming composition >>
The composition for forming a protective film such as the composition for forming a protective film (IV-1) can be obtained by blending each component for constituting the composition.
The order of addition at the time of blending each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
The method of mixing each component at the time of compounding is not particularly limited, from a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.
The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30 ° C.

◎ Method for Manufacturing Semiconductor Device The method for manufacturing a semiconductor device of the present invention is a method for manufacturing a semiconductor chip with a protective film according to the above-described method for manufacturing a semiconductor chip with a protective film. A pulling step for 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 the protective film is pulled away from the support sheet by performing the push-up with the pin, the remaining of the push-up mark due to the pin in the protective film can be suppressed. 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 according to the present invention is suitable for separating the semiconductor chip with a protective film from the support sheet by pushing it up with a pin in the separating step.

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

  In the separation step, for example, as shown in FIG. 4, a pin (projection) 70 protrudes from a push-up portion (not shown) in the semiconductor device manufacturing apparatus, and the tip end portion of the pin 70 makes a contact with the support sheet 10. A force is applied from the substrate 11 side. Thus, the semiconductor chip 8 with a protective film is pushed up by applying a force to the semiconductor chip 8 with the protective film through the support sheet 10 by the pins 70. Further, the semiconductor chip 8 with the protective film is pulled up (pick up) from the support sheet 10 by pulling up the semiconductor chip 8 with the protective film by the pulling means 71 in the semiconductor device manufacturing apparatus. Here, the pulling direction of the semiconductor chip 8 with the protective film is indicated by an arrow II. An example of the pulling means 71 is a vacuum collet.

  The push-up conditions such as the protrusion amount (push-up amount) of the pin 70, the protrusion speed (push-up speed), and the hold time (lifting waiting time) of the protruding state may be adjusted as appropriate, and are not particularly limited. The number of pins 70 to be protruded with respect to one semiconductor chip 8 with a protective film is not particularly limited, and may be one, for example, two or more, and may be selected as appropriate.

  In this step, the protective film 131 ′ that is applied with force through the support sheet 10 by the pin 70 has a high elastic modulus. Accordingly, on the surface 131b 'of the protective film 131' on the support sheet 10 side, the remaining of the push-up marks due to the pins 70 is suppressed.

  Further, since the elastic modulus of the protective film 131 ′ is high, the semiconductor film 8 with the protective film is prevented from being attached to the storage portion by the protective film 131 ′ during the storage.

  Here, the separation step in the case of using the processed laminated structure 101 ′ shown in FIG. 1 has been described, but for example, in the case of using another processed laminated structure such as that shown in FIG. The separation step can be performed in a similar manner.

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

The components used for the production of the protective film-forming composition are shown below.
[Energy ray curable component (a)]
(A2) -1: Tricyclodecane dimethylol diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., bifunctional ultraviolet curable compound, molecular weight 304)
[Polymer (b) having no energy ray curable group]
(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) An acrylic resin (weight average molecular weight 400000, glass transition temperature 8 ° C.).
[Photoinitiator (c)]
(C) -1: 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (“Irgacure (registered trademark) 369” manufactured by BASF)
(C) -2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Irgacure (registered by BASF)) 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 pigment (Pigment Blue 15: 3), 18 parts by mass of isoindolinone yellow pigment (Pigment Yellow 139), and 50 parts by mass of anthraquinone red pigment (Pigment Red 177) And a pigment obtained by pigmenting so that the total amount of the three kinds of 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 of 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, epoxy equivalent of 255 to 260 g / eq)
・ Thermosetting agent (h2)
(H2) -1: Dicyandiamide (thermally active latent epoxy resin curing agent, “ADEKA HARDNER EH-3636AS” manufactured by ADEKA, amount of active hydrogen 21 g / eq)
[Curing accelerator (i)]
(I) -1: 2-Phenyl-4,5-dihydroxymethylimidazole (“Cureazole 2PHZ” manufactured by Shikoku Chemicals)

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

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. In the oven, the test piece was heated for 2 hours under the conditions of 130 ° C. and 30% RH (relative humidity), and then the test piece was taken out from the oven and cooled to 23 ° C. Next, the distance between measurements marked on the test piece was measured again, and the expansion / contraction rate (%) in the MD direction of the substrate was calculated according to the following formula.
Expansion rate (%) = (distance between measurements after heating / distance between measurements before heating) × 100

  Separately, the base material is cut into a size of 22 mm short side and 110 mm long side so that the short side is in the MD direction and the long side is in the CD direction. did. Using this test piece, the stretch rate (%) in the CD direction of the substrate was calculated in the same manner as in the test piece for measuring the stretch rate in the MD direction.

The tensile modulus of the substrate 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.
Subsequently, based on JISK7127: 1999, the tensile elasticity modulus (Young's modulus) of the said test piece in 23 degreeC was measured. Specifically, the test piece was installed in a tensile tester (“Autograph AG-IS 500N” manufactured by Shimadzu Corporation), the distance between chucks was set to 100 mm, and then the tensile test was performed at a speed of 200 mm / min. A test was performed and the tensile modulus (MPa) was measured. The tensile modulus was measured in both the MD direction and the CD direction of the substrate.

<Manufacture of composite sheet for forming protective film>
[Production Example 1]
(Production of protective film-forming composition (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 the values shown in Table 1. The composition for protective film formation (IV-1) whose solid content concentration is 50 mass% was prepared by stirring at 23 degreeC. In addition, description with "-" of the column of the containing component in Table 1 means that the composition (IV-1) for protective film formation does not contain the component.

(Manufacture of protective film-forming film)
The protective film-forming composition (IV-1) obtained above was applied to the release-treated surface of a release film obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and the film was formed at 120 ° C. By partial drying, an energy ray-curable protective film-forming film having a thickness of 15 μm was produced.

(Production of pressure-sensitive adhesive composition (I-2))
Acrylic polymer (100 parts by mass, solid content), trifunctional xylylene diisocyanate crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (6.6 parts by mass, solid content), and photopolymerization initiator (2 -Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropan-1-one, “Irgacure® 127” manufactured by BASF) (3 Energy ray-curable pressure-sensitive adhesive composition (I-2) having a solid content concentration of 30% by mass and further containing methyl ethyl ketone as a solvent. The acrylic polymer includes acrylic acid-2-ethylhexyl (hereinafter abbreviated as “2EHA”) (80 parts by mass) and acrylic acid-2-hydroxyethyl (hereinafter abbreviated as “HEA”) (20 mass). Part) is reacted with 2-methacryloyloxyethyl isocyanate (21.4 parts by mass, an amount in which the isocyanate group is 80 mol% with respect to 100 mol% of the hydroxyl group in HEA). It is an energy ray-curable acrylic polymer having a weight average molecular weight of 1100000 obtained.

(Manufacture of support sheet)
The pressure-sensitive adhesive composition (I-2) obtained above is applied to the release-treated surface of a release film obtained by releasing one side of a 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.
Subsequently, the support sheet was manufactured by bonding a flexible polypropylene film (thickness: 80 μm) to the exposed surface of the pressure-sensitive adhesive layer.

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

(Manufacture of composite sheet for protective film formation)
Next, the release film on the pressure-sensitive adhesive layer of the support sheet is removed, and the exposed surface of the film for forming a protective film obtained above is bonded to the surface of the exposed pressure-sensitive adhesive layer. A protective film-forming composite sheet was produced by laminating a protective film-forming film and a release film in this thickness direction in this order. Table 2 shows the structure of the obtained protective sheet-forming composite sheet.

[Production Example 2]
(Manufacture of protective film-forming composition)
Polymer (b) -1 having no energy ray curable group, filler (d) -1, coupling agent (e) -1, colorant (g) -1, epoxy resin (h1) -1, epoxy Resin (h1) -2, epoxy resin (h1) -3, thermosetting agent (h2) -1 and curing accelerator (i) -1 are shown in Table 1 with their contents (solid content, parts by mass). A thermosetting composition for forming a protective film having a solid 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.

(Manufacture of protective film-forming film)
In place of the protective film-forming composition (IV-1), the thermosetting protection was carried out in the same manner as in Production Example 1, except that the thermosetting protective film-forming composition obtained above was used. A film forming film was produced.

(Production of pressure-sensitive adhesive composition and support sheet)
A pressure-sensitive adhesive composition and a support sheet were produced in the same manner as in Production Example 1.

(Manufacture of composite sheet for protective film formation)
Next, the release film on the pressure-sensitive adhesive layer of the support sheet is removed, and the exposed surface of the thermosetting protective film-forming film obtained above is bonded to the surface of the exposed pressure-sensitive adhesive layer to form a substrate. The composite sheet for protective film formation in which the adhesive layer, the film for protective film formation, and the peeling film were laminated | stacked in this order in these thickness directions was produced. Table 2 shows the structure of the composite sheet for forming a protective film.

[Production Example 3]
(Production of protective film forming composition and protective film forming film)
By the same method as in Production Example 2, a protective film-forming composition and a protective film-forming film were produced.

(Production of pressure-sensitive adhesive composition (I-4))
Contains an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (“Takenate D110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) (20 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent. The non-energy ray-curable pressure-sensitive adhesive composition (I-4) containing 30% by mass of the solid content 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). Is 600,000.

(Manufacture of support sheet)
The non-energy ray-curable pressure-sensitive adhesive composition (I-4) obtained above is applied to the release-treated surface of a release film obtained by releasing one side of a 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 support sheet was manufactured by bonding a heat-resistant polypropylene film (thickness: 80 μm) to the exposed surface of the pressure-sensitive adhesive layer.

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

(Manufacture of composite sheet for protective film formation)
Next, the release film on the pressure-sensitive adhesive layer of the support sheet is removed, and the exposed surface of the film for forming a protective film obtained above is bonded to the surface of the exposed pressure-sensitive adhesive layer. A protective film-forming composite sheet was produced by laminating a protective film-forming film and a release film in this thickness direction in this order. Table 2 shows the structure of the obtained protective sheet-forming composite sheet.

[Example 1]
<Manufacture of semiconductor chip with protective film>
A semiconductor chip with a protective film was manufactured by the above-described manufacturing method (1) according to the following procedure.

(Laminated structure forming process)
A 12 inch silicon wafer (thickness 300 μm) with a back grind tape affixed to the circuit forming surface and the back surface opposite to the circuit forming surface being a # 2000 ground surface is provided with a laser saw from the ground surface side. (“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.
Then, 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. while forming this protective film. A laminated structure was formed by sticking a composite sheet for forming a protective film on the ground surface of the silicon wafer through a film for use.

(Expanding process)
After mounting the ring frame on the laminated structure obtained above, the back grind tape is removed, and the protective film forming film is cooled at 0 ° C., and using an expander (“DDS2300” manufactured by Disco) The laminated structure was expanded in the surface direction of the protective film-forming film by pushing up the table under the conditions of 20 mm / sec and a push-up amount of 20 mm. As a result, the protective film-forming 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 formation process)
The cut film for forming a protective film was irradiated with ultraviolet rays under the conditions of an illuminance of 230 mW / cm ² and a light amount of 170 mJ / cm ² to form a protective film, thereby obtaining a semiconductor chip with a protective film.

<Evaluation of semiconductor chip with support sheet and protective film>
(Heat shrinkability (restorability of support sheet))
After the above-described expanding step, this peripheral portion was heated by blowing hot air on the peripheral portion of the support sheet under the conditions of a temperature of 220 ° C. and a rotational speed of 5 mm / ° using a dryer. Next, the peripheral edge portion of the support sheet after heating was visually observed, and it was confirmed whether or not the slack produced in the support sheet due to the expansion was eliminated by the shrinkage of the support sheet by heating, and evaluation was performed according to the following criteria. The results are shown in Table 2.
○: The slack is eliminated.
X: The slack is not eliminated and the semiconductor chip with a protective film after expansion cannot be transported or stored.

(Residual suppression of push-up marks by pins on the protective film)
At the time of the above-described expanding process and evaluation of heat shrinkability, pick-up of a semiconductor chip with a protective film was attempted by the following procedure using a laminated structure after processing, in which no problem was observed.
In other words, a push-pull gauge (“MODEL-RE” manufactured by Aiko Engineering Co., Ltd.) with a No. 5 needle set as a pin used for push-up, the push-up amount is 1.5 mm, and a semiconductor with a protective film over the support sheet I pushed the tip up. And the protective film was visually observed, the presence or absence of the needle mark was confirmed, and it evaluated according to the following reference | standard. The results are shown in Table 2.
○: There is no needle mark.
X: Needle marks are present.

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

(Protective film formation 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 amount 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 protective film-forming film was cooled at 0 ° C. at the time of expansion using the laminated structure obtained after forming the protective film. Instead of this, the protective film was cut in the same manner as in Example 1 except that the temperature of the protective film was 30 ° C., and the silicon wafer was divided at the site of the modified layer, and the size was 3 mm. A semiconductor chip with a protective film was obtained as a plurality of semiconductor chips of 3 mm.

<Evaluation of semiconductor chip with support sheet and protective film-forming film>
(Heat shrinkability (restorability of the support sheet) and suppression of the remaining lift marks by pins in the 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]
<Manufacture of semiconductor chip with protective film-forming film>
According to the conventional method described with reference to FIG. 6, a semiconductor chip with a protective film-forming film was manufactured according to the following procedure.

A laminated structure is formed in the same manner as in Example 1 except that the protective film-forming composite sheet obtained in Production Example 2 is used in place of the protective film-forming composite sheet obtained in Production Example 1. 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 obtain a plurality of 3 mm × 3 mm in size. Individual semiconductor chips were obtained.
Thus, a semiconductor chip with a protective film-forming film was obtained.

<Evaluation of semiconductor chip with support sheet and protective film-forming film>
(Heat shrinkability (restorability of the support sheet) and suppression of the remaining lift marks by pins in the 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 remaining 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]
<Manufacture of semiconductor chip with protective film>
A semiconductor chip with a protective film was manufactured by the conventional method described with reference to FIG.

A laminated structure is formed in the same manner 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 1. did.
Next, the obtained laminated structure was heated at 130 ° C. for 2 hours to cure the protective film-forming film and form a protective film.
Then, in place of the laminated structure before curing the protective film-forming film, the laminated structure was the same as in Example 1 except that the laminated structure after curing the protective film-forming film was used. The structure was expanded, the protective film was cut, and the silicon wafer was divided at the modified layer to obtain a plurality of semiconductor chips having a size of 3 mm × 3 mm.
Thus, a semiconductor chip with a protective film was obtained.

<Evaluation of semiconductor chip with support sheet and protective film>
(Heat shrinkability (restorability of the support sheet) and suppression of remaining push-up marks by pins in 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)
After mounting the ring frame on the laminated structure, and before curing the protective film-forming film by heating, the arrangement position of the protective film-forming composite sheet was recorded. Subsequently, the protective film-forming film is cured (formation of the protective film) by heating, and after the protective film-forming film is cooled and before the laminated structure is expanded, the composite for forming the protective film is formed. The position of the sheet was recorded. And from the record of these arrangement positions, the sinking amount (slack amount) of the protective film-forming composite sheet accompanying the curing of the protective film-forming film was calculated and evaluated according to the following criteria. The results are shown in Table 2. In addition, description of "-" in the column of the evaluation result in Table 2 means that the item has not been evaluated.
◯: The sinking amount is less than 0.5 mm.
X: The sinking amount is 0.5 mm or more.

  As is clear from the above results, in Examples 1 and 2, the protective film-forming film was not cured by heat and was cured by irradiation with energy rays, so that the support sheet was not loosened immediately after curing. . On the other hand, the slack produced in the support sheet by the expanding process was eliminated by heating the peripheral edge of the support sheet, and the heat shrinkability (restorability of the support sheet) was good. This is because a flexible substrate is used. Moreover, in Examples 1-2, since the elasticity modulus of the protective film was high, the remaining of the push-up trace by a pin was suppressed. And in Example 1, the film for protective film formation was fully cut | disconnected in the target location after the expansion process, and the semiconductor wafer was also divided | segmented favorably. In Example 2, after the expanding step, the protective film was sufficiently cut at the target location, and the semiconductor wafer was also well divided. In Examples 1 and 2, since the protective film-forming film is not thermally 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 thermally cured, the support sheet was not loosened before the expansion. Moreover, since the flexible base material was used like the case of Example 1, the heat shrink property was favorable. However, since the protective film-forming film was not cured and the protective film was not formed, in the protective film-forming film having a low elastic modulus, it was not possible to suppress the remaining of the push-up marks due to the pins. In Comparative Example 1, after expansion, the protective film-forming film was sufficiently cut at the target location, and the semiconductor wafer was also well divided. In Comparative Example 1, as in Example 1, since the protective film-forming film is not thermally cured, the support sheet (base material) does not need to have heat resistance, and the support sheet has heat resistance. Is not yet evaluated.

  In Comparative Example 2, the protective film-forming film was heat-cured, but since a heat-resistant substrate was used, the support sheet was not slackened immediately after curing. On the other hand, the slack produced in the support sheet due to the expansion has not been eliminated by heating the peripheral edge of the support sheet, and the heat shrinkability was poor. As a result, the subsequent steps cannot be performed, and the remaining suppression of the push-up marks by the pins in 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 for manufacturing semiconductor devices.

  DESCRIPTION OF SYMBOLS 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' ... modification of semiconductor wafer Layer, 8 '... semiconductor wafer

Claims (4)

A laminate in which an energy ray curable protective film forming film is provided on a support sheet, a semiconductor wafer is provided on the protective film forming film, and a modified layer is formed inside the semiconductor wafer. A laminated structure forming step of forming a structure;
After the laminated structure forming step,
The laminated structure is expanded in the surface direction of the protective film forming film, the protective film forming film is cut, and the semiconductor wafer is divided at a portion of the modified layer, and a plurality of semiconductor chips are formed. An expanding process to obtain;
A protective film forming step of obtaining a semiconductor chip with a protective film by irradiating the protective film forming film after cutting with an energy ray to form a protective film, or
A protective film forming step of forming a protective film by irradiating the protective film forming film with energy rays;
The laminated structure after forming the protective film is expanded in the surface direction of the protective film to cut the protective film, and to divide the semiconductor wafer at a portion of the modified layer, so that a plurality of protective films A method for producing a semiconductor chip with a protective film, comprising: an expanding step for obtaining a semiconductor chip with a protective film. Before the laminated structure forming step,
The modified layer is formed inside the semiconductor wafer by irradiating the semiconductor wafer before the protective film-forming film is provided with a laser beam so as to focus on the focal point set inside the semiconductor wafer. The manufacturing method of the semiconductor chip with a protective film of Claim 1 which has a modified layer formation process. The support sheet is provided with a pressure-sensitive adhesive layer on a substrate,
The manufacturing method of the semiconductor chip with a protective film of Claim 1 or 2 with which the said film for protective film formation is directly contacted and provided in the said 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 3,
A method for manufacturing a semiconductor device, comprising: a separation step of separating the semiconductor chip with a protective film from the support sheet.

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