JP2024025169A - Sheet for protective membrane formation and manufacturing method of workpiece with protective membrane - Google Patents

Abstract

To provide a sheet for protective membrane formation which is capable of suppressing contamination of a work caused by a protective membrane formation film while preventing manufacture efficiency of a workpiece with a protective membrane when adhering the protective membrane formation film to the work, eliminates the need to process a release film when using the sheet for protective membrane formation and is capable of recycling the used release film, the sheet for protective membrane formation comprising the protective membrane formation film capable of forming the protective membrane and the release film.SOLUTION: A sheet for protective membrane formation comprises a first release film, a second release film which has the release power higher than that of the first release film, and a protective membrane formation film provided therebetween. In the sheet for protective membrane formation, two or more protective membrane formation films are disposed in a length direction of the first release film, and a planar shape of the protective membrane formation film is circular or substantially circular. A diameter of the protective membrane formation film is settled within a specific range, and any one of or both the first release film and the second release film have no slit substantially.SELECTED DRAWING: None

Description

The present invention relates to a protective film forming sheet and a method for manufacturing a workpiece with a protective film.

Some wafers, such as semiconductor wafers and insulator wafers, have circuits formed on one surface (circuit surface) and further have protruding electrodes such as bumps on that surface (circuit surface). Such a wafer is divided into chips and mounted on the circuit board by connecting the protruding electrodes to connection pads on the circuit board. In such wafers and chips, the surface opposite to the circuit surface (back surface) is sometimes protected with a protective film in order to suppress damage such as cracking.
Further, in the process of manufacturing a semiconductor device, a semiconductor device panel, which will be described later, is used as a workpiece, and in order to suppress the occurrence of warpage or cracks in this panel, some portion of the panel may be protected with a protective film.

In such cases, for example, a protective film forming film for forming a protective film is pasted on the desired part of the workpiece, such as the back side of the wafer, and the workpiece is then processed to produce workpieces such as chips. A protective film is prepared, and if necessary, the protective film-forming film is cured, and the protective film-forming film or the protective film is cut, thereby comprising a workpiece and a protective film provided on any part of the workpiece. Manufacture workpieces with attached parts. An example of a workpiece with a protective film is a semiconductor chip with a protective film, which includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip.

When producing a workpiece with a protective film, the workpiece is generally circular in planar shape, so the planar shape of the protective film forming film immediately before being pasted is also often circular. A protective film-forming film used in such applications may be provided with release films on both sides, for example. In order to continuously attach the protective film-forming film to the workpiece, a plurality of circularly punched protective film-forming films are placed between two long release films. A protective film forming sheet arranged along the longitudinal direction is widely used.

FIG. 1(a) is a plan view schematically showing an example of such a conventional protective film forming sheet, and FIG. 1(b) is an I of the protective film forming sheet shown in FIG. 1(a). FIG. 2 is a diagram schematically showing a cross section taken along the -I line.

The protective film forming sheet 9 includes a first release film 92, a second release film 93, and a protective film forming film 91 provided between the first release film 92 and the second release film 93. There is. Both the first release film 92 and the second release film 93 are long. FIG. 1A is a plan view of the protective film forming sheet 9 viewed from above on the first release film 92 side.
Furthermore, in the thickness direction of the protective film forming sheet 9, the film passes from one surface 92a of the first release film 92 to one surface 93a of the second release film 93, and enters the inside of the second release film 93. Two or more circular notches 99 are provided that reach up to. That is, the cut 99 penetrates the first release film 92 and the protective film forming film 91 in the thickness direction thereof. Thereby, for example, the protective film forming film 91 is divided into two or more first regions 911 each having a circular planar shape and a second region 912 other than the first regions 911 . The first release film 92 is similarly divided. The second region 912 of the protective film-forming film is a surplus portion, and is removed from the second release film 93 together with the first release film 92 attached thereto before the protective film-forming sheet 9 is used. On the other hand, the first region 911 of the protective film forming film is the part to be attached to the workpiece. When using the protective film-forming sheet 9, the first release film 92 attached to the first region 911 of the protective film-forming film is removed, so that one surface 911a of the first region 911 of the protective film-forming film is This becomes an exposed surface, and the first region 911 is attached to the work on this surface 911a (exposed surface). Note that the operation of removing a surplus portion such as the second region 912 of the protective film forming film is sometimes referred to as "removal" in the field.

The protective film forming sheet 9 can be obtained by, for example, producing a laminated sheet in which a protective film forming film 91 is provided between a first peeling film 92 and a second peeling film 93, and then applying the protective film to the laminated sheet. It can be manufactured by applying a blade from the first release film 92 side therein to form two or more circular cuts 99.

In this way, as a long protective film forming sheet provided with a plurality of circularly punched protective film forming films, for example, in the above-mentioned scrap lifting process, the protective film forming film is attached to the workpiece. A film has been disclosed that is highly effective in suppressing so-called scum-raising defects, in which the pasted portion of the protective film is removed together with the surplus portion of the protective film-forming film (see Patent Document 1).

JP2022-32570A

When attaching a protective film-forming film whose planar shape is circular or approximately circular (described later) to the circular surface of a workpiece, if the size (area) of the protective film-forming film is too large, it may cause damage from the outer periphery of the workpiece. The protective film forming film protrudes, and this protruding portion of the protective film forming film adheres to the outer periphery (side surface) of the workpiece, contaminating the workpiece. In that case, the protective film-coated workpiece cannot be normally manufactured, and furthermore, the inside of the protective film forming film application device may be contaminated. On the other hand, if the size (area) of the protective film forming film is too small, the usable area of the workpiece becomes smaller than necessary, and the manufacturing efficiency of the workpiece with the protective film decreases.

On the other hand, from the viewpoint of effective resource utilization and environmental protection, it is desirable to collect and reuse components such as release films that are unnecessary when using the protective film-forming film. However, a release film in which cuts are formed, such as the first release film 92, cannot be reused after being removed from the protective film forming film. Furthermore, in order to improve the versatility of a protective film forming sheet with cuts, such as the protective film forming sheet 9, when the protective film forming sheet is shipped as a product, no cuts are formed in it. When a purchaser uses a protective film forming sheet, a notch may be formed in the protective film forming sheet. In that case, cutting waste of the release film may be generated in the purchaser's equipment as the release film is punched out, which may contaminate the purchaser's equipment.

Considering these circumstances, as a protective film forming sheet consisting of two or more circular or nearly circular protective film forming films with release films provided on both sides, it is possible to attach the protective film forming film to the workpiece. In some cases, contamination of the workpiece by the protective film-forming film can be suppressed without reducing the production efficiency of the workpiece with the protective film, and when using the protective film-forming sheet, there is no need to cut out the release film, and after use, A protective film-forming sheet whose release film can be reused is extremely useful.
On the other hand, conventional protective film forming sheets such as the one disclosed in Patent Document 1 cannot be said to satisfy all of these requirements.

The present invention is a protective film-forming sheet comprising a protective film-forming film and a release film provided on both surfaces of the protective film-forming film, wherein the protective film-forming film is capable of forming a protective film in a workpiece with a protective film. , the workpiece is obtained by processing the workpiece, and when the protective film-forming film is attached to the workpiece, the workpiece is prevented from being contaminated by the protective film-forming film without reducing the manufacturing efficiency of the workpiece with the protective film. It is an object of the present invention to provide a protective film-forming sheet that can be used without the need for punching of a release film when using the protective film-forming sheet, and that allows the used release film to be reused. A further object of the present invention is to provide a method for manufacturing a workpiece with a protective film using the above-mentioned sheet for forming a protective film.

In order to solve the above problems, the present invention employs the following configuration.
[1] A sheet for forming a protective film, wherein the sheet for forming a protective film includes a first release film, a second release film having a greater peeling force than the first release film, and a combination of the first release film and the a protective film-forming film provided between a second release film, and two or more of the protective film-forming films include one of the first release film and one of the second release film. is arranged along the direction, the planar shape of the protective film forming film is circular or approximately circular, and the diameter of the protective film forming film is 135 mm or more and less than 150 mm, 185 mm or more and less than 200 mm, 285 mm or more and less than 300 mm, or 435 mm or more and less than 450 mm, and one or both of the first release film and the second release film does not substantially have a cut at a position that coincides with the outer periphery of the protective film forming film. , a sheet for forming a protective film.
[2] The difference between the peeling force of the second release film with respect to the protective film forming film and the peeling force of the first release film with respect to the protective film forming film is 30 mN/100 mm or more and less than 200 mN/100 mm, The peeling force of the first release film against the protective film forming film is 20 mN/100 mm or more, and the peeling force of the second release film against the protective film forming film is 500 mN/100 mm or less, according to [1]. Sheet for forming a protective film.

[3] The protective film forming sheet according to [1] or [2], wherein the first release film does not substantially have the cuts.
[4] A method for manufacturing a workpiece with a protective film, wherein the workpiece with a protective film includes a workpiece and a protective film provided on one surface of the workpiece. , the workpiece is obtained by processing a workpiece, the planar shape of the workpiece is circular, the diameter of the workpiece is 6 inches, 8 inches, 12 inches, or 18 inches, and the protective film is is formed from the protective film forming film in the protective film forming sheet according to any one of [1] to [3], and when the workpiece has a diameter of 6 inches, When the diameter of the protective film forming film is 135 mm or more and less than 150 mm, and the diameter of the workpiece is 8 inches, the diameter of the protective film forming film is 185 mm or more and less than 200 mm, and the diameter of the workpiece is 12 inches. In this case, the diameter of the protective film forming film is 285 mm or more and less than 300 mm, and when the diameter of the workpiece is 18 inches, the diameter of the protective film forming film is 435 mm or more and less than 450 mm, and the When the protective film-forming film is curable, the cured product of the protective film-forming film is the protective film, and when the protective film-forming film is non-curable, any part of the workpiece The protective film forming film after being affixed to the protective film forming sheet is the protective film, and the manufacturing method includes a first peeling step of peeling the first release film from the protective film forming film in the protective film forming sheet. After the first peeling step, the surface of the protective film forming film on the side where the first peeling film was provided is removed without causing the outer peripheral part of the protective film forming film to protrude from the outer peripheral part of the workpiece. a first attaching step of producing a first laminate in which the protective film forming film or the protective film is provided on the workpiece by attaching it to one side of the work; and after the first attaching step, the a second peeling step of peeling the second release film from the protective film-forming film or the protective film in the first laminate; and after the second peeling step, the second release film of the protective film-forming film or the protective film is removed. 2. By pasting a processing sheet for processing the workpiece on the side where the release film was provided, the processing sheet, the protective film forming film or the protective film, and the workpiece can be separated from each other. A second pasting step of manufacturing a second laminate configured by laminating these in the thickness direction, and after the second pasting step, the workpiece is manufactured by processing the workpiece. and a cutting step of cutting the protective film-forming film or the protective film after the second pasting step, and when the protective film-forming film is curable, the method further comprises: 2. After the peeling step, a curing step of forming the protective film by curing the protective film forming film.

According to the present invention, the protective film forming sheet is provided with a protective film forming film and a release film provided on both sides thereof, and the protective film forming film is capable of forming a protective film in a workpiece with a protective film. The workpiece is obtained by processing the workpiece, and when the protective film-forming film is attached to the workpiece, the workpiece can be processed by the protective film-forming film without reducing the production efficiency of the workpiece with the protective film. Provided is a protective film-forming sheet that can suppress contamination, does not require punching of the release film when the protective film-forming sheet is used, and allows the used release film to be reused. Furthermore, according to the present invention, there is provided a method for manufacturing a workpiece with a protective film using the above-mentioned sheet for forming a protective film.

FIG. 2 is a diagram schematically showing an example of a conventional protective film forming sheet, in which (a) is a plan view and (b) is a cross-sectional view taken along the line II in (a). 1 is a diagram schematically showing an example of a sheet for forming a protective film according to an embodiment of the present invention, in which (a) is a plan view and (b) is a cross-sectional view taken along the line II-II in (a). FIG. 2 is a cross-sectional view schematically showing another example of a protective film forming sheet according to an embodiment of the present invention. It is a sectional view showing typically still another example of the sheet for protective film formation concerning one embodiment of the present invention. It is a figure which shows typically another example of the sheet for protective film formation which concerns on one Embodiment of this invention, (a) is a top view, (b) is a sectional view taken on the III-III line in (a). It is. It is a sectional view showing typically still another example of the sheet for protective film formation concerning one embodiment of the present invention. It is a sectional view showing typically still another example of the sheet for protective film formation concerning one embodiment of the present invention. It is a sectional view showing typically still another example of the sheet for protective film formation concerning one embodiment of the present invention. FIG. 2 is a cross-sectional view schematically illustrating an example of a method for manufacturing a workpiece with a protective film according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically illustrating an example of a method for manufacturing a workpiece with a protective film according to an embodiment of the present invention. FIG. 3 is a cross-sectional view for schematically explaining another example of the method for manufacturing a work piece with a protective film according to an embodiment of the present invention. FIG. 3 is a cross-sectional view for schematically explaining another example of the method for manufacturing a work piece with a protective film according to an embodiment of the present invention.

◇Sheet for forming a protective film The sheet for forming a protective film according to an embodiment of the present invention includes a first release film, a second release film having a greater peeling force than the first release film, and the first release film. a protective film-forming film provided between the second release film and the two or more protective film-forming films, one of the first release film and one of the second release film. arranged along the longitudinal direction, the planar shape of the protective film-forming film is circular or approximately circular, and the diameter of the protective film-forming film is 135 mm or more and less than 150 mm, 185 mm or more and less than 200 mm, or 285 mm or more and less than 300 mm. , or 435 mm or more and less than 450 mm, and one or both of the first release film and the second release film substantially has a cut at a position that coincides with the outer periphery of the protective film forming film. do not.
The protective film forming film in the protective film forming sheet of this embodiment can form a protective film on one surface of a workpiece having a circular planar shape.

The diameter of the protective film forming film in the protective film forming sheet of this embodiment is 135 mm or more and less than 150 mm, 185 mm or more and less than 200 mm, 285 mm or more and less than 300 mm, or 435 mm or more and less than 450 mm, so that the workpiece of the protective film forming film is When the film is attached to a workpiece, contamination of the workpiece by the protective film-forming film can be suppressed without reducing the production efficiency of the workpiece with the protective film. Further, when using the protective film forming sheet, punching of the release film is not necessary.

The protective film forming film in the protective film forming sheet of this embodiment is a film used for providing a protective film on any part of the workpiece to protect the workpiece.
The protective film forming film is soft and can be attached to the workpiece before being processed into the workpiece.

In this embodiment, examples of the work include a wafer, a semiconductor device panel, and the like. A semiconductor device panel is something that is handled in the manufacturing process of semiconductor devices, and a specific example is a semiconductor device in which one or more electronic components are sealed with a sealing resin. An example of this is a structure in which these semiconductor devices are arranged planarly within a circular area.
In this specification, a processed workpiece is referred to as a "workpiece processed product." For example, when the workpiece is a semiconductor wafer, the workpiece may be a semiconductor chip.

In this specification, "wafer" refers to a semiconductor wafer composed of elemental semiconductors such as silicon, germanium, and selenium, and compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; An example is an insulator wafer made of an insulator.
A circuit is formed on one side of a workpiece, typically a wafer, and in this specification, the side of the workpiece on which the circuit is formed is referred to as a "circuit side." The surface of the workpiece opposite to the circuit surface is referred to as the "back surface."
The wafer is divided into chips by means such as dicing. In this specification, as in the case of a wafer, the surface of the chip on which a circuit is formed is referred to as the "circuit surface", and the surface of the chip opposite to the circuit surface is referred to as the "back surface".
It is preferable that protruding electrodes such as bumps and pillars are provided on the circuit surface of the workpiece. Preferably, the protruding electrode is made of solder.

By using the protective film forming film in the protective film forming sheet of this embodiment, a chip with a protective film including a chip and a protective film provided on the back surface of the chip can be manufactured.
Prior to manufacturing the chip with a protective film, by using the protective film forming film, a wafer with a protective film forming film including a wafer and a protective film forming film provided on the back surface of the wafer is manufactured. can.

Furthermore, by using the work piece with the protective film, a substrate device can be manufactured.
In this specification, the term "substrate device" refers to a structure in which a workpiece with a protective film is connected to a circuit board. An example of the substrate device is one in which a workpiece with a protective film is flip-chip connected to a connection pad on a circuit board at a protruding electrode on a circuit surface thereof. For example, if a semiconductor wafer is used as the workpiece, the substrate device may be a semiconductor device on which a semiconductor chip with a protective film is mounted. The semiconductor chip with a protective film includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip.

In the protective film-forming sheet of the present embodiment, two or more protective film-forming films are arranged along the longitudinal direction of one first release film and one second release film, so that protection is achieved. The membrane-forming film can be continuously attached to the workpiece.

In the protective film-forming sheet of the present embodiment, one or both of the first release film and the second release film substantially has a cut at a position that coincides with the outer periphery of the protective film-forming film. By not doing so, these release films can be reused after use.

The protective film forming sheet of this embodiment is preferably long, and such a protective film forming sheet is suitable for being wound up into a roll and stored (as a roll of the protective film forming sheet). It is.

<<First release film>>
The first release film may be a known film.
More specifically, the first release film includes, for example, one in which one or both surfaces of the base material for a release film is a release-treated surface.
The release-treated surface can be formed by subjecting the surface of the release film base material to a release treatment using a release agent.

Examples of the constituent material of the release film base material include various resins.
Preferred resins as constituent materials for the release film base include, for example, polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyolefins such as polyethylene and polypropylene; polyurethane; and polyimide.

The number of resins constituting the release film base material may be one, or two or more, and when there are two or more, the combination and ratio thereof can be arbitrarily selected.

The release agent may be a known release agent.
Preferred release agents include, for example, alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, or wax-based release agents.
The release agent is preferably an alkyd-based, silicone-based, or fluorine-based release agent in terms of heat resistance.

The first release film may be composed of one layer (single layer) or may be composed of two or more layers. When the first release film 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.

In this specification, not only in the case of the first release film, "the plurality of layers may be the same or different from each other" means "all the layers may be the same or all the layers may be different". ``The layers may be the same, or only some of the layers may be the same.'' Furthermore, ``the layers are different from each other'' means ``at least one of the constituent materials and thickness of each layer is different from each other.'' It means that.

The first release film has a smaller release force than the second release film described below. In this specification, the peeling force of a release film is not limited to the case of the first release film, and refers to the release force of the release film and the material attached to the release film (herein referred to as "applied material"). In the case of a laminate of (1) and (2), it means the force required when the release film is peeled off from the adhesive. That is, when comparing the force when peeling the first release film from the object to which it is applied and the force when peeling the second release film from the object to which it is applied, it is found that If the attachment of the film is the same, and the manner of attachment of the first release film and the attachment is the same as the manner of attachment of the second release film and the attachment, then the The force required to peel off the first release film from its applied material is smaller than the force required to peel the second release film from its applied material.
In the protective film forming sheet, the peeling force of the first release film to the protective film forming film is smaller than the peeling force of the second release film to the protective film forming film.

The peel force of the first release film against the protective film forming film is preferably 20 mN/100 mm or more, and may be, for example, any of 40 mN/100 mm or more, 60 mN/100 mm or more, and 80 mN/100 mm or more. When the peeling force of the first release film is equal to or greater than the lower limit, the effect of suppressing unintended peeling of the first release film from the protective film-forming film in the protective film-forming sheet becomes higher.

The peeling force of the first release film against the protective film forming film may be, for example, 140 mN/100 mm or less, preferably 120 mN/100 mm or less, more preferably 100 mN/100 mm or less, and 80 mN/100 mm or less. More preferably, it is 100 mm or less. The smaller the peeling force of the first release film is, the easier the first release film can be peeled off from the protective film-forming film when the protective film-forming sheet is used.

The peeling force of the first release film with respect to the protective film forming film can be adjusted as appropriate within a range set by any combination of any of the above lower limits and any of the above upper limits.
In one embodiment, the peeling force of the first release film may be, for example, any one of 20 to 140 mN/100 mm, 40 to 140 mN/100 mm, 60 to 140 mN/100 mm, and 80 to 140 mN/100 mm. , 20-120mN/100mm, 40-120mN/100mm, 60-120mN/100mm, and 80-120mN/100mm, or 20-100mN/100mm, 40-100mN/100mm, 60-100mN /100 mm, and 80 to 100 mN/100 mm, or may be any of 20 to 80 mN/100 mm, 40 to 80 mN/100 mm, and 60 to 80 mN/100 mm. However, these are examples of the peeling force of the first peeling film.

The peeling force of the first release film with respect to the protective film forming film was determined by the method described in the examples below, at a peeling speed of 1000 mm/min in an environment of a temperature of 23°C and a relative humidity of 50%. The peeling force is when the first release film is peeled from the protective film forming film (180° peeling is performed) so that the surfaces of the protective film forming films that were in contact with each other form an angle of 180°. preferable.

<Adhesion force between the first release film and the stainless steel plate>
When the surface of the first release film on the protective film forming film side (for example, the release-treated surface) and the surface of the stainless steel (SUS) plate are attached, the adhesive force between the first release film and the stainless steel plate is , preferably 0 mN/25 mm or more and less than 50 mN/25 mm, more preferably 0 mN/25 mm or more and less than 20 mN/25 mm, even more preferably 0 mN/25 mm or more and less than 10 mN/25 mm, and 0 mN/25 mm or more and less than 5 mN It is particularly preferable that it is less than /25 mm. The first peeling film is peeled off from the protective film forming film using a protective film forming sheet provided with such a first peeling film (for example, in the first peeling step in the method for manufacturing a workpiece with a protective film described below). ), when this peeled first release film is wound up into a roll, the winding misalignment of the first release film is suppressed. Moreover, a protective film forming sheet provided with such a first release film can be manufactured at a lower cost.
In the protective film forming sheet, at least the area where the protective film forming film is not laminated on the surface of the first release film on the protective film forming film side has the above-mentioned adhesive force (0 mN/25 mm or more and less than 50 mN/25 mm). The entire area (entire surface) of the surface may have the above-mentioned adhesive force (0 mN/25 mm or more and less than 50 mN/25 mm).
The adhesive force between the first release film and the stainless steel plate can be measured by the 90° peeling method described later in Examples.

The peeling force of the first release film and the adhesion force between the first release film and the stainless steel plate are determined by, for example, the type and amount of the release agent used for peeling the surface of the base material for the release film, and the release treatment method. It can be adjusted by adjusting etc.

The first release film is preferably elongated, such as in the form of a strip. When the first release film is long, and the second release film is similarly long, it is possible to increase the number of protective film-forming films in the protective film-forming sheet.
Preferred examples of the first release film include those having a width of 150 to 500 cm and a length of 20 to 200 m.

The first release film may have a cut or substantially no cut, regardless of its position (area), and for example, coincides with the outer periphery of the protective film-forming film. There may be a notch at the position where the cut is made, or there may be substantially no notch. However, it is preferable that the first release film has substantially no notches at a position that coincides with the outer periphery of the protective film-forming film, and it is preferable that the first release film has substantially no notches regardless of the position (area). is more preferable. Such a first release film is suitable for reuse when the sheet for forming a protective film is peeled off from the film for forming a protective film during use, collected, and reused. Furthermore, in such a first release film, the problem that a portion of the protective film-forming film remains as an afterimage at the notch site after being peeled off from the protective film-forming film is suppressed.

In this specification, the first release film does not substantially have any cuts, regardless of the position on the first release film, or even if the first release film has no cuts. , means that the depth of the cut is less than 1 μm.

In the protective film forming sheet, the position of the first release film that coincides with the outer periphery of the protective film forming film means, for example, the position of the laminate of the first release film and the protective film forming film on the protective film forming film side. When viewed from above and viewed in plan, it refers to the position of the surface of the first release film on the protective film forming film side that overlaps with the outer peripheral portion (circumferential portion when viewed in plan) of the protective film forming film.
The protective film-forming sheet, which has a cut in the first release film at a position that coincides with the outer periphery of the protective film-forming film, is prepared by punching the protective film-forming film in advance into the desired shape (here, it is punched into a circular or approximately circular shape). (processing), it is easy to make. On the other hand, the protective film-forming film of the present embodiment is produced by the method described below, so that the first release film does not substantially have such cuts.

The thickness of the first release film is preferably 20 to 100 μm, more preferably 25 to 80 μm. When the thickness of the first release film is equal to or greater than the lower limit, the mechanical strength of the first release film becomes higher. When the thickness of the first release film is less than or equal to the upper limit value, it becomes easier to wind up the protective film forming sheet or the first release film into a roll.
Here, the "thickness of the first release film" means the thickness of the entire first release film. For example, the thickness of the first release film consisting of multiple layers refers to all means the total thickness of the layers.

In this specification, "thickness" is not limited to the case of the first release film, and unless otherwise specified, "thickness" is expressed as the average thickness measured at five randomly selected locations on the object. This value can be obtained using a constant pressure thickness measuring device according to JIS K7130.

<<Second release film>>
The second release film may be a known film.
The second release film is similar to the first release film, except that it has a greater release force against the protective film forming film than the first release film.

The peeling force of the second release film against the protective film forming film is preferably 500 mN/100 mm or less, and may be, for example, any of 400 mN/100 mm or less, 300 mN/100 mm or less, and 200 mN/100 mm or less. The peeling force of the second release film is equal to or less than the upper limit, so that the first release film in the protective film-forming sheet can be peeled from the protective film-forming film (for example, in the production of a workpiece with a protective film, which will be described later). (first peeling step in the method), attaching a protective film forming film provided with a second release film to the workpiece (e.g., first attaching step in the method for manufacturing a workpiece with a protective film described below), and then forming a protective film. When peeling the second release film from the film or protective film (for example, the second peeling step in the method for producing a workpiece with a protective film described below), suppressing the peeling of the protective film forming film or the protective film from the workpiece. The effect will be higher.

The peeling force of the second release film against the protective film forming film is preferably 80 mN/100 mm or more, and may be either 110 mN/100 mm or more, or 130 mN/100 mm or more, for example. The greater the peeling force of the second release film, the higher the effect of suppressing unintended peeling of the second release film from the protective film forming film or the protective film.

The peeling force of the second release film can be adjusted as appropriate within a range set by any combination of any of the above lower limits and any of the above upper limits.
In one embodiment, the peeling force of the second release film may be, for example, any of 80 to 500 mN/100 mm, 80 to 400 mN/100 mm, 80 to 300 mN/100 mm, and 80 to 200 mN/100 mm; It may be any of 110-500mN/100mm, 110-400mN/100mm, 110-300mN/100mm, and 110-200mN/100mm, or 130-500mN/100mm, 130-400mN/100mm, 130-300mN/ It may be either 100 mm or 130 to 200 mN/100 mm. However, these are examples of the peeling force of the second release film.

The peeling force of the second release film with respect to the protective film forming film was determined by the method described in the Examples below, at a peeling speed of 1000 mm/min in an environment of a temperature of 23°C and a relative humidity of 50%. The peeling force is when the protective film-forming film is peeled off from the second release film (180° peeling is performed) so that the surfaces of the protective film-forming films that were in contact with each other form an angle of 180°. preferable. At this time, the protective film-forming film is preferably peeled off from the second release film in the form of a laminate with a reinforcing adhesive film attached to the surface opposite to the second release film.

<Difference in peeling force between the second release film and the first release film>
The difference between the peeling force of the second release film with respect to the protective film forming film and the peeling force of the first release film with respect to the protective film forming film (herein referred to as "the peeling force of the second release film and the first release film"). For example, the difference may be 15 mN/100 mm or more, preferably 30 mN/100 mm or more, more preferably 50 mN/100 mm or more, and 70 mN/100 mm or more. It is even more preferable. Since the difference in peeling force between the second release film and the first release film is greater than or equal to the lower limit value, the first release film can be more easily peeled off from the protective film-forming film when the protective film-forming sheet is used. .

The difference in peel force between the second release film and the first release film is preferably less than 200 mN/100 mm, and may be, for example, either 150 mN/100 mm or less, or 100 mN/100 mm or less. By setting the difference in peeling force between the second release film and the first release film within such a range, the peeling force of the first release film against the protective film forming film and the peeling force of the second release film against the protective film forming film can be reduced. , it becomes easier to adjust the values within each of the above-mentioned numerical ranges.

The difference in peeling force between the second release film and the first release film can be adjusted as appropriate within a range set by any combination of any of the above lower limits and any of the above upper limits.
For example, the peel force difference may be 15 mN/100 mm or more and less than 200 mN/100 mm, but preferably 30 mN/100 mm or more and less than 200 mN/100 mm, 50 mN/100 mm or more and less than 200 mN/100 mm, and 70 mN/100 mm. It may be more than 200 mN/100 mm, or it may be 30 to 150 mN/100 mm, 50 to 150 mN/100 mm, and 70 to 150 mN/100 mm, or it may be 30 to 100 mN/100 mm, or 50 to 100 mN/100 mm. ~100mN/100mm, and 70~100mN/100mm. However, these are examples of the difference in peeling force.

<Adhesion force between the second release film and the stainless steel plate>
The second release film also preferably has the same adhesive force with the stainless steel plate as the first release film, for the same reason as the first release film.
In other words, when the surface of the second release film on the protective film forming film side (for example, the release treated surface) and the surface of the stainless steel (SUS) plate are attached, the adhesion between the second release film and the stainless steel plate is The bonding force is preferably 0 mN/25 mm or more and less than 50 mN/25 mm, more preferably 0 mN/25 mm or more and less than 20 mN/25 mm, even more preferably 0 mN/25 mm or more and less than 10 mN/25 mm, and 0 mN/25 mm. It is particularly preferable that it is at least 5 mN/25 mm. Using a protective film-forming sheet provided with such a second release film, the second release film is peeled off from the protective film-forming film or the protective film (for example, in the method for manufacturing a workpiece with a protective film described below). (2) Peeling step) When the peeled second release film is wound up into a roll, the winding shift of the second release film is suppressed. Moreover, a protective film forming sheet provided with such a second release film can be manufactured at a lower cost.
In the protective film-forming sheet, at least the area on which the protective film-forming film or the protective film is not laminated on the protective film-forming film side or the surface on the protective film side of the second release film has the above-mentioned adhesive force (0 mN/ 25 mm or more and less than 50 mN/25 mm), and the entire area (entire surface) of the surface may have the above-mentioned adhesive force (0 mN/25 mm or more and less than 50 mN/25 mm).
The adhesion between the second release film and the stainless steel plate can be measured in the same way as for the first release film.

The release force of the second release film and the adhesion between the second release film and the stainless steel plate can be adjusted in the same way as for the first release film.

The second release film may have a cut or substantially no cut, regardless of its position (area); for example, it may coincide with the outer periphery of the protective film forming film. There may be a notch at the position where the cut is made, or there may be substantially no notch. The second release film having substantially no cuts is suitable for reuse when the sheet for forming a protective film is peeled off from the protective film forming film or the protective film when the sheet is used, collected, and reused. Furthermore, in such a second release film, after being peeled off from the protective film-forming film or the protective film, the problem that a part of the protective film-forming film or the protective film remains as an afterimage at the cut site is suppressed.

In this specification, "the second release film does not substantially have cuts" means that the second release film has no cuts at all, or even if it has cuts, regardless of the position on the second release film. , means that the depth of the cut is less than 1 μm.
The position of the second release film in the protective film-forming sheet that coincides with the outer peripheral portion of the protective film-forming film means the same as in the case of the first release film described above.

However, in the protective film-forming sheet of this embodiment, one or both of the first release film and the second release film substantially has a cut at a position that coincides with the outer periphery of the protective film-forming film. I don't have it. In the protective film forming sheet of the present embodiment, it is preferable that the first release film does not substantially have the above-mentioned cuts. Such a protective film forming sheet has higher handling properties.

The thickness of the second release film is preferably 20 to 100 μm, more preferably 25 to 90 μm. When the thickness of the second release film is equal to or greater than the lower limit, the mechanical strength of the second release film becomes higher. When the thickness of the second release film is less than or equal to the upper limit value, it becomes easier to wind up the protective film forming sheet or the second release film into a roll.
Here, the "thickness of the second release film" means the thickness of the entire second release film. For example, the thickness of the second release film consisting of multiple layers refers to the total thickness of the second release film. means the total thickness of the layers.

The difference ([protective film The thickness of the area where the forming film is laminated (laminated area) - [thickness of the area where the protective film forming film is not laminated (non-laminated area)] is preferably less than 10 μm, and preferably less than 5 μm. It is more preferable that When the protective film-forming sheet is wound up into a roll, the protective film-forming film may not be placed in the same position in the radial direction of the roll. Further, pressure is applied to the roll of the protective film forming sheet in the radial direction of the roll. Therefore, in such a case, curling marks are likely to occur on the protective film forming film. On the other hand, in the second release film, since there is no or very small difference in thickness, the occurrence of curling marks on the protective film forming film is suppressed.

The difference ([protective film The thickness of the area where the forming film is laminated (laminated area) - [thickness of the area where the protective film forming film is not laminated (non-laminated area)] is preferably -10 μm or more, and - It is more preferably 5 μm or more, and even more preferably 0 μm or more. When the difference is greater than or equal to the lower limit, the second release film can be more easily peeled off from the protective film forming film.

The second release film is similar to the first release film except for the above-mentioned points. Therefore, any further detailed description of the second release film will be omitted.

<<Protective film forming film>>
The protective film-forming film may be the same as known protective film-forming films, except that its planar shape is circular or approximately circular, and its diameter is specified within a specific range.

The planar shape of the protective film-forming film, that is, the shape of the main surface of the protective film-forming film when viewed from above is circular or approximately circular.
In this specification, "substantially circular" means a shape that is not circular but is close enough to a circle that there is no problem in considering it as circular.
For example, in a non-circular shape (that is, a shape that is not a perfect circle), the shortest line segment that connects two points on the outer circumference and passes through the center of gravity (or the center in some cases) A shape in which the length of the line segment is 0.993 times or more the length of the longest line segment is approximately circular. For example, in the case of an ellipse, if the length of the minor axis is 0.993 times or more the length of the major axis, the ellipse is approximately circular.
In addition, in this specification, the length of the longest line segment among the line segments connecting two points on the outer periphery and passing through the center of gravity (or the center in some cases) is defined as the length of the approximately circular line segment. Regarded as the diameter of the shape. For example, in the case of an ellipse, the length of the major axis is considered the diameter.

The planar shape of the protective film-forming film is preferably an ellipse. By using such a planar protective film-forming film, contamination of the workpiece by the protective film-forming film can be more easily suppressed.

When attaching a protective film-forming film to one side of a workpiece using a protective film-forming sheet, it is usually applied in the longitudinal direction of the protective film-forming sheet (in other words, in the longitudinal direction of the second release film). ), the first release film is peeled off from the protective film-forming film, and then the protective film-forming film on the second release film is attached to one side of the workpiece. That is, when the protective film-forming film is attached to the workpiece, the protective film-forming film and the second release film are pulled in the longitudinal direction of the second release film, so the length of the protective film-forming film can be extended in this direction. . In this direction, when the length of the protective film-forming film is extended, it is preferable that the planar shape of the protective film-forming film in such an extended state is circular. By doing so, the protective film-forming film can be attached so that the workpiece having a circular planar shape can be used more efficiently while suppressing contamination of the workpiece by the protective film-forming film. For this purpose, in the protective film forming sheet, the short axis direction of the ellipse of the protective film forming film, which has an elliptical planar shape, must match the longitudinal direction (length direction) of the first release film and the second release film. (In other words, the long axis direction of the ellipse must match the direction perpendicular to the longitudinal direction of the first release film and the second release film (that is, the width direction or the width direction)).

In the protective film forming sheet of this embodiment, the lower limit of the diameter of the protective film forming film is 15 mm smaller than the diameter of the workpiece to which the protective film forming film is attached. On the other hand, the upper limit value of the diameter of the protective film-forming film is a value smaller than the diameter of the workpiece to which the protective film-forming film is attached. More specifically, it is as follows.

The protective film forming film having a diameter of 285 mm or more and less than 300 mm is intended for attachment to a workpiece having a diameter of 12 inches (300 mm).
The diameter of such a protective film forming film may be, for example, 288 mm or more and less than 300 mm, 291 mm or more and less than 300 mm, and 294 mm or more and less than 300 mm, or 285 to 296 mm, 285 to 293 mm, and 285 to 290 mm. The length may be either 288 to 296 mm. However, these are examples of the diameter of a protective film forming film for attachment to a workpiece having a diameter of 12 inches (300 mm).

The protective film forming film having a diameter of 135 mm or more and less than 150 mm is intended for attachment to a workpiece having a diameter of 6 inches (150 mm).
The diameter of such a protective film forming film may be, for example, 138 mm or more and less than 150 mm, 141 mm or more and less than 150 mm, and 144 mm or more and less than 150 mm, or 135 to 146 mm, 135 to 143 mm, and 135 to 140 mm. The length may be either 138 to 146 mm. However, these are examples of the diameter of a protective film forming film for attachment to a workpiece having a diameter of 6 inches (150 mm).

The protective film forming film having a diameter of 185 mm or more and less than 200 mm is intended for attachment to a workpiece having a diameter of 8 inches (200 mm).
The diameter of such a protective film forming film may be, for example, 188 mm or more and less than 200 mm, 191 mm or more and less than 200 mm, and 194 mm or more and less than 200 mm, or 185 to 196 mm, 185 to 193 mm, and 185 to 190 mm. The length may be either 188 to 196 mm. However, these are examples of the diameter of a protective film forming film for attachment to a workpiece having a diameter of 8 inches (200 mm).

The protective film forming film having a diameter of 435 mm or more and less than 450 mm is intended for attachment to a workpiece having a diameter of 18 inches (450 mm).
The diameter of such a protective film forming film may be, for example, 438 mm or more and less than 450 mm, 441 mm or more and less than 450 mm, and 444 mm or more and less than 450 mm, or 435 to 446 mm, 435 to 443 mm, and 435 to 440 mm. It may be either 438 to 446 mm. However, these are examples of the diameter of a protective film forming film for attachment to a workpiece having a diameter of 18 inches (450 mm).

The protective film forming film is provided between the first release film and the second release film. That is, the protective film-forming sheet is constructed by laminating a second release film, a protective film-forming film, and a first release film in this order in their thickness direction.
One protective film-forming sheet includes two or more protective film-forming films, and these two or more protective film-forming films are combined with one first release film and one second release film. arranged along the longitudinal direction.

The two or more protective film-forming films included in one protective film-forming sheet may all be the same, all different, or only some of them may be the same, In terms of high versatility, it is preferable that they all be the same.
In this specification, two protective film-forming films are compared, and when any one or more of the diameter, composition, and thickness of these protective film-forming films differ from each other, these protective film-forming films are compared with each other. be different.

In the protective film forming sheet, it is preferable that two or more protective film forming films are arranged in a line along the longitudinal direction of one first release film and one second release film.

The protective film forming film may be curable or non-curable. That is, the protective film-forming film may function as a protective film when cured, or may function as a protective film in an uncured state.
The curable protective film-forming film may be either thermosetting or energy ray curable, or may have both thermosetting and energy ray curable properties.

As used herein, the term "energy ray" refers to electromagnetic waves or charged particle beams that have energy quanta. Examples of energy rays include ultraviolet rays, radiation, electron beams, and the like. The ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, fusion lamp, xenon lamp, black light, or LED lamp as an ultraviolet source. The electron beam can be generated by an electron beam accelerator or the like.
In this specification, "energy ray curable" means a property that hardens when irradiated with energy rays, and "non-energy ray curable" means a property that does not harden even when irradiated with energy rays. do.
As used herein, "non-curable" means a property that does not harden by any means such as heating or irradiation with energy rays. The non-curable protective film-forming film can be considered to be a protective film after it is provided (formed) on the intended object.

When forming a protective film by thermally curing the protective film-forming film, unlike curing by irradiation with energy rays, the protective film-forming film can be cured sufficiently by heating even if it is thick. Because it hardens, it can form a protective film with high protection ability. Moreover, by using a normal heating means such as a heating oven, a large number of protective film-forming films can be heated and thermally cured at once.
When the protective film-forming film is cured by irradiation with energy rays to form a protective film, unlike when it is thermally cured, the film or sheet laminated to the protective film-forming film during curing is heat resistant. There is no need to have Moreover, the protective film-forming film can be cured in a short time by irradiation with energy rays.
When the protective film-forming film is used as a protective film without being cured, the curing step can be omitted, so a workpiece with a protective film can be manufactured through a simplified process.

The protective film forming film may be composed of one layer (single layer) or may be composed of two or more layers. When the protective film forming film 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.

When the protective film-forming film is composed of two or more layers, the protective film may warp due to poor adhesion between each layer or differences in the ease of expansion and contraction of each layer. Problems such as peeling from the workpiece may occur, and from the viewpoint of suppressing such problems, it is preferable that the protective film-forming film consists of one layer.
A protective film forming film consisting of one layer is preferable because it can be easily manufactured with high thickness uniformity and has a high degree of freedom in design.

The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 80 μm, and particularly preferably 5 to 60 μm. When the thickness of the protective film-forming film is equal to or greater than the lower limit, a protective film with higher protective ability can be formed. By setting the thickness of the protective film-forming film to be less than or equal to the upper limit value, the thickness of the protective film can be prevented from becoming excessive.
Here, the "thickness of the protective film-forming film" means the thickness of the entire protective film-forming film. For example, the thickness of a protective film-forming film consisting of multiple layers refers to all means the total thickness of the layers.

<<Composition for forming a protective film>>
The protective film-forming film can be formed using a protective film-forming composition containing the constituent materials. For example, a protective film-forming film can be formed by applying a protective film-forming composition to the surface to be formed, and drying as necessary. The content ratio of components that do not vaporize at room temperature in the protective film-forming composition is usually the same as the content ratio of the components in the protective film-forming film. As used herein, "normal temperature" means a temperature that is not particularly cooled or heated, that is, a normal temperature, and includes, for example, a temperature of 18 to 28°C.

A thermosetting protective film forming film can be formed using a thermosetting protective film forming composition, an energy beam curable protective film forming film can be formed using an energy beam curable protective film forming composition, The non-curable protective film-forming film can be formed using a non-curable protective film-forming composition. In this specification, when the protective film-forming film has both thermosetting and energy ray curable properties, the contribution of the heat curing of the protective film forming film to the energy ray curing is If the contribution is greater than the contribution of , the protective film-forming film is treated as a thermosetting film. On the other hand, if the contribution of energy ray curing of the protective film forming film to the formation of the protective film is greater than the contribution of heat curing, the protective film forming film is treated as energy ray curing.

In the protective film-forming film, the ratio of the total content of one or more of the below-mentioned components of the protective film-forming film to the total mass of the protective film-forming film does not exceed 100% by mass.
Similarly, in the composition for forming a protective film, the ratio of the total content of one or more components described below in the composition for forming a protective film to the total mass of the composition for forming a protective film is 100 mass. Do not exceed %.

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

Drying conditions for the composition for forming a protective film are not particularly limited. However, when the composition for forming a protective film contains a solvent described below, it is preferable to dry it by heating. The composition for forming a protective film containing a solvent is preferably dried by heating at, for example, 70 to 130°C for 10 seconds to 5 minutes. However, it is preferable to heat-dry the thermosetting protective film-forming composition so that the composition itself and the thermosetting protective film-forming film formed from the composition are not thermally cured.

Hereinafter, a thermosetting protective film-forming film, an energy ray-curable protective film-forming film, and a non-curing protective film-forming film will be sequentially explained.

◎Thermosetting protective film forming film The curing conditions for forming a protective film by thermosetting the thermosetting protective film forming film are as long as the degree of curing is such that the protective film can sufficiently exhibit its function. It is not particularly limited, and may be appropriately selected depending on the type of thermosetting protective film forming film.
For example, the heating temperature during thermosetting of the thermosetting protective film-forming film is preferably 100 to 200°C. The heating time during the thermosetting is preferably 0.5 to 5 hours.

A protective film-forming film at room temperature is heated to a temperature exceeding room temperature, and then cooled to room temperature to form a protective film-forming film after heating and cooling. When comparing the hardness of the protective film-forming film before heating and the hardness of the protective film-forming film before heating at the same temperature, if the protective film-forming film after heating and cooling is harder, this protective film-forming film is thermosetting. .

Preferred thermosetting protective film-forming films include, for example, those containing a polymer component (A), a thermosetting component (B), a filler (D), and a colorant (I).
The polymer component (A) is a component that can be considered to be formed by a polymerization reaction of a polymerizable compound.
The thermosetting component (B) is a component that can undergo a curing (polymerization) reaction using heat as a reaction trigger. Note that in this specification, the polymerization reaction also includes a polycondensation reaction.

<Thermosetting protective film forming composition (III)>
A preferred composition for forming a thermosetting protective film includes, for example, a thermosetting protective film containing the polymer component (A), the thermosetting component (B), the filler (D), and the colorant (I). Forming composition (III) (in this specification, it may be simply abbreviated as "composition (III)"), and the like.

[Polymer component (A)]
The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, etc. to the thermosetting protective film-forming film. Note that in this specification, the polymer compound also includes a product of a polycondensation reaction.

The composition (III) and the thermosetting protective film-forming film may contain only one type of polymer component (A), or may contain two or more types, and in the case of two or more types, Their combination and ratio can be selected arbitrarily.

Examples of the polymer component (A) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins, with acrylic resins being preferred.

Examples of the acrylic resin include polymers of one or more (meth)acrylic acid esters; (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, etc. Examples include copolymers of more than one type of monomer.

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

The acrylic resin may have a functional group capable of bonding with other compounds, such as a vinyl group, (meth)acryloyl group, amino group, hydroxyl group, carboxy group, or isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F), which will be described later, or may be bonded directly to another compound without using a crosslinking agent (F).

In this embodiment, a thermoplastic resin other than acrylic resin (hereinafter sometimes simply abbreviated as "thermoplastic resin") may be used alone as the polymer component (A) without using the acrylic resin. It may be used together with an acrylic resin. By using the thermoplastic resin, it may become easier for the thermosetting protective film-forming film to follow the uneven surface of the adherend (for example, the rough back surface of a wafer).

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

The composition (III) and the thermosetting protective film-forming film may contain only one type of thermoplastic resin, or may contain two or more types, and when they are two or more types, Combinations and ratios can be selected arbitrarily.

In composition (III), the ratio of the content of polymer component (A) to the total content of all components other than the solvent is 5 to 65% by mass, regardless of the type of polymer component (A). The amount is preferably 5 to 45% by mass, and more preferably 5 to 45% by mass.
This content means that the content ratio of the polymer component (A) to the total mass of the thermosetting protective film-forming film is independent of the type of the polymer component (A); This is synonymous with preferably 5 to 65% by mass, more preferably 5 to 45% by mass.
This is based on the fact that in the process of removing the solvent from a resin composition containing a solvent to form a resin film, the amounts of components other than the solvent usually do not change. In this case, the content ratios of the components other than the solvent are the same. Therefore, in this specification, the content of components other than the solvent will be described only in the resin film obtained by removing the solvent from the resin composition, not only in the case of the thermosetting protective film forming film. .

The polymer component (A) may also correspond to the thermosetting component (B). In the present invention, when the composition (III) contains components corresponding to both the polymer component (A) and the thermosetting component (B), the composition (III) contains the polymer component (A) and the thermosetting component (B). (A) and a thermosetting component (B).

[Thermosetting component (B)]
The thermosetting component (B) is a component for thermosetting the thermosetting protective film forming film.
The composition (III) and the thermosetting protective film-forming film may contain only one type of thermosetting component (B), or may contain two or more types, and in the case of two or more types. , their combination and ratio can be selected arbitrarily.

Examples of the thermosetting component (B) include epoxy thermosetting resins, thermosetting polyimide resins, unsaturated polyester resins, and the like, with epoxy thermosetting resins being preferred.
In this specification, the thermosetting polyimide resin is a general term for a polyimide precursor and a thermosetting polyimide, which form a polyimide resin by thermosetting.

(Epoxy thermosetting resin)
The epoxy thermosetting resin consists of an epoxy resin (B1) and a thermosetting agent (B2).
The composition (III) and the thermosetting protective film-forming film may contain only one type of epoxy thermosetting resin, or may contain two or more types, and in the case of two or more types, Their combination and ratio can be selected arbitrarily.

・Epoxy resin (B1)
Examples of the epoxy resin (B1) include known ones, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, Examples include epoxy compounds having two or more functionalities, such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin.

As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group may be used.

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

・Thermosetting agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, a group in which an acid group is anhydrified, and the like. It is preferably a group, and more preferably a phenolic hydroxyl group or an amino group.

Among the thermosetting agents (B2), examples of phenolic curing agents having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins, aralkyl type phenolic resins, etc. .
Among the thermosetting agents (B2), examples of amine-based curing agents having an amino group include dicyandiamide.

The thermosetting agent (B2) may have an unsaturated hydrocarbon group.

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

The content of the thermosetting agent (B2) in the thermosetting protective film forming film is preferably 0.1 to 25 parts by mass, and 0.1 to 25 parts by mass, based on 100 parts by mass of the epoxy resin (B1). More preferably, it is 5 to 10 parts by mass. When the content of the thermosetting agent (B2) is at least the lower limit, curing of the thermosetting protective film forming film progresses more easily. When the content of the thermosetting agent (B2) is below the upper limit, the moisture absorption rate of the thermosetting protective film-forming film is reduced, and the reliability of the package obtained using the protective film-forming film is improved. Improve more.

The content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) in the thermosetting protective film forming film is the same as that of the polymer component (A) and the thermosetting component. It is preferably 40 to 75 parts by weight, more preferably 50 to 70 parts by weight, based on 100 parts by weight of the total content of the sexual component (B). By having the content of the thermosetting component (B) in such a range, both the effect of using the thermosetting component (B) and the effect of using the polymer component (A) can be achieved. Easy to play.

[Filler (D)]
By containing the filler (D) in the thermosetting protective film forming film, the thermal expansion coefficient of the thermosetting protective film forming film and the protective film can be easily adjusted, and this thermal expansion coefficient is used as the target for forming the protective film. By optimizing the process for the object, the reliability of the protective film-coated workpiece obtained using the protective film-forming film is further improved. Moreover, when the thermosetting protective film-forming film contains the filler (D), the moisture absorption rate of the protective film can be reduced and the heat dissipation properties can be improved.

The composition (III) and the thermosetting protective film-forming film may contain only one kind of filler (D), or may contain two or more kinds, and when they are two or more kinds, they The combination and ratio can be arbitrarily selected.

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 titanium oxide (titanium white), aluminum oxide (alumina), silica, talc, calcium carbonate, red iron, silicon carbide, boron nitride, etc.; beads made of spherical inorganic fillers; Examples include surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, and the like.

The content ratio of the filler (D) in the thermosetting protective film-forming film to the total mass of the thermosetting protective film-forming film is preferably 45 to 80% by mass, and preferably 65 to 80% by mass. It is more preferable that there be. When the ratio is within this range, it becomes easier to adjust the thermal expansion coefficients of the thermosetting protective film-forming film and the protective film, and the protective film-coated workpiece obtained using the protective film-forming film can be easily adjusted. The reliability of the workpiece is further improved.

[Colorant (I)]
The light transmittance of the thermosetting protective film-forming film and the protective film can be easily adjusted by containing the colorant (I).

Examples of the colorant (I) include known ones such as inorganic pigments, organic pigments, and organic dyes.

The composition (III) and the thermosetting protective film-forming film may contain only one type of colorant (I), or may contain two or more types, and when they are two or more types, they The combination and ratio can be arbitrarily selected.

When using the colorant (I), the content of the colorant (I) in the thermosetting protective film-forming film may be adjusted as appropriate depending on the purpose. For example, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film and adjusting the light transmittance of the thermosetting protective film-forming film, the thermosetting protective film-forming film or the protective film can be On the other hand, when laser printing is performed, the print visibility can be adjusted. Furthermore, by adjusting the content of the colorant (I) in the thermosetting protective film forming film, it is possible to improve the design of the protective film and to make grinding marks on the back surface of the wafer less visible. Considering these points, the content ratio of colorant (I) in the thermosetting protective film-forming film to the total mass of the thermosetting protective film-forming film is 0.1 to 7.5% by mass. The amount is preferably 0.1 to 5% by mass, and more preferably 0.1 to 5% by mass. When the ratio is equal to or higher than the lower limit, the effect of using the colorant (I) can be more prominently obtained. For example, when the thermosetting protective film-forming film is peeled off from the adherend, it can be easily confirmed visually whether or not the thermosetting protective film-forming film remains on the adherend. When the ratio is equal to or less than the upper limit, excessive use of the colorant (I) is suppressed.

[Curing accelerator (C)]
The composition (III) and the thermosetting protective film forming film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing speed of the composition (III).
Preferred curing accelerators (C) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole; , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and other imidazoles (where one or more hydrogen atoms are other than hydrogen atoms) (imidazole substituted with a group of Examples include tetraphenylboron salts such as tetraphenylborate.

The composition (III) and the thermosetting protective film-forming film may contain only one kind of curing accelerator (C), or may contain two or more kinds, and in the case of two or more kinds, Their combination and ratio can be selected arbitrarily.

When using a curing accelerator (C), the content of the curing accelerator (C) in the thermosetting protective film forming film is 0.01 parts by mass based on 100 parts by mass of the thermosetting component (B). The amount is preferably 5 parts by weight, more preferably 0.1 to 3 parts by weight. When the content of the curing accelerator (C) is at least the lower limit, the effect of using the curing accelerator (C) can be more significantly obtained. By setting the content of the curing accelerator (C) at or below the upper limit value, for example, the highly polar curing accelerator (C) can be deposited in the thermosetting protective film forming film under high temperature and high humidity conditions. The effect of suppressing migration to the adhesive interface side with the body and segregation becomes higher. As a result, the reliability of a work piece with a protective film obtained using the protective film forming film is further improved.

[Coupling agent (E)]
The composition (III) and the thermosetting protective film forming film may contain a coupling agent (E). By using a coupling agent (E) that has a functional group that can react with an inorganic compound or an organic compound, the adhesion of the protective film formed from the thermosetting protective film forming film to the adherend can be improved. be able to. Further, by using the coupling agent (E), the water resistance of the protective film is improved 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 polymer component (A), thermosetting component (B), etc., and is preferably a silane coupling agent. More preferred.

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-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples include dimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.

The composition (III) and the thermosetting protective film-forming film may contain only one type of coupling agent (E), or may include two or more types, and in the case of two or more types, Their combination and ratio can be selected arbitrarily.

When using the coupling agent (E), the content of the coupling agent (E) in the thermosetting protective film forming film is 100% by mass of the total content of the polymer component (A) and the thermosetting component (B). The amount is preferably 0.01 to 7 parts by weight, more preferably 0.02 to 3 parts by weight. When the content of the coupling agent (E) is at least the lower limit, the dispersibility of the filler (D) in the resin can be improved, and the adhesiveness of the thermosetting protective film forming film to the adherend can be improved. The effects of using the coupling agent (E), such as improvement in When the content of the coupling agent (E) is at most the upper limit, the generation of outgas is further suppressed.

[Crosslinking agent (F)]
As the polymer component (A), a polymer having a functional group such as a vinyl group, a (meth)acryloyl group, an amino group, a hydroxyl group, a carboxy group, an isocyanate group, etc. that can be bonded to other compounds, such as the above-mentioned acrylic resin, is used. In this case, the composition (III) and the thermosetting protective film-forming film may contain a crosslinking agent (F). The crosslinking agent (F) is a component for crosslinking the functional groups in the polymer component (A) by bonding them with other compounds, and by crosslinking in this way, the thermosetting protective film forming film is formed. Adhesion and cohesion 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), etc. can be mentioned.

The composition (III) and the thermosetting protective film-forming film may contain only one type of crosslinking agent (F), or may contain two or more types, and when they are two or more types, they The combination and ratio can be arbitrarily selected.

When using the crosslinking agent (F), in the composition (III), the content of the crosslinking agent (F) is 0.01 to 20 parts by mass based on 100 parts by mass of the polymer component (A). The amount is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass. When the content of the crosslinking agent (F) is at least the lower limit, the effect of using the crosslinking agent (F) can be more significantly obtained. Excessive use of the crosslinking agent (F) is suppressed because the content of the crosslinking agent (F) is below the upper limit value.

[Energy ray curable resin (G)]
The composition (III) and the thermosetting protective film forming film may contain an energy ray curable resin (G). Since the thermosetting protective film forming film contains the energy ray curable resin (G), its properties can be changed by irradiation with energy rays.

The energy ray curable resin (G) is an energy ray curable compound, or an energy ray curable oligomer or an energy ray curable polymer (polymer) that can be considered to be synthesized from an energy ray curable compound.
Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth)acryloyl group are preferred.

The composition (III) and the thermosetting protective film-forming film may contain only one kind of energy ray-curable resin (G), or may contain two or more kinds, and are two or more kinds. In this case, their combination and ratio can be selected arbitrarily.

When using the energy ray curable resin (G), the content ratio of the energy ray curable resin (G) to the total mass of the thermosetting protective film forming film is 1 to 1. It is preferably 30% by weight, more preferably 5 to 25% by weight.

[Photopolymerization initiator (H)]
When the composition (III) and the thermosetting protective film forming film contain the energy ray curable resin (G), in order to efficiently advance the polymerization reaction of the energy ray curable resin (G), the composition (III) and the thermosetting protective film forming film contain a photopolymerization initiator. (H) may be contained.

Examples of the photopolymerization initiator (H) in composition (III) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, and the like. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-1-(4-(4 -(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, etc. Acetophenone compounds; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzylphenyl sulfide, tetramethylthiuram monosulfide, etc. Sulfide compounds; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl ; Dibenzyl; Benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 1-chloroanthraquinone, 2-chloroanthraquinone Examples include quinone compounds such as.
Examples of the photopolymerization initiator (H) include photosensitizers such as amines.

The composition (III) and the thermosetting protective film-forming film may contain only one type of photopolymerization initiator (H), or may contain two or more types, and in the case of two or more types. , their combination and ratio can be selected arbitrarily.

When using a photopolymerization initiator (H), the content of the photopolymerization initiator (H) in the thermosetting protective film forming film is based on 100 parts by mass of the energy ray curable resin (G). It is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight.

[General-purpose additive (J)]
The composition (III) and the thermosetting protective film-forming film may contain a general-purpose additive (J) within a range that does not impair the effects of the present invention.
The general-purpose additive (J) may be any known one and can be arbitrarily selected depending on the purpose, and is not particularly limited, but preferable examples include a plasticizer, an antistatic agent, an antioxidant, a gettering agent, Examples include ultraviolet absorbers.

The composition (III) and the thermosetting protective film-forming film may contain only one kind of general-purpose additive (J), or may contain two or more kinds, and in the case of two or more kinds, Their combination and ratio can be selected arbitrarily.
The content of the general-purpose additive (J) in the composition (III) and the thermosetting protective film-forming film is not particularly limited, and may be appropriately selected depending on the purpose.

[solvent]
It is preferable that composition (III) further contains a solvent. Composition (III) containing a solvent has good handling properties.
In this specification, unless otherwise specified, the term "solvent" is a concept that includes not only a substance that dissolves the target component but also a dispersion medium that disperses the target component.

The solvent is not particularly limited, but preferable examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol. ; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
Composition (III) may contain only one kind of solvent, or may contain two or more kinds of solvents, and when they are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

Among the solvents contained in composition (III), more preferable solvents include, for example, methyl ethyl ketone, toluene, ethyl acetate, and the like, from the standpoint that the components contained in composition (III) can be mixed more uniformly.

The content of the solvent in composition (III) is not particularly limited, and may be appropriately selected depending on the types of components other than the solvent, for example.

<Method for producing thermosetting protective film forming composition (III)>
Composition (III) can be obtained by blending the components for constituting it.
The order in which each component is added when blending is not particularly limited, and two or more components may be added at the same time.
The method of mixing each component at the time of compounding is not particularly limited, and may be any known method, such as mixing by rotating a stirrer or stirring blade; mixing by using a mixer; or mixing by applying ultrasonic waves. You can select it as appropriate.
The temperature and time during addition and mixing of each component are not particularly limited as long as each component does not deteriorate, and may be adjusted as appropriate, but the temperature is preferably 15 to 30°C.

◎Energy ray curable protective film forming film When applying the energy ray curable protective film forming film to the desired part of the workpiece and curing it with energy rays to form a protective film, the curing conditions are such that the protective film is sufficiently There is no particular limitation as long as the degree of curing is sufficient to exhibit its function, and it may be selected as appropriate depending on the type of energy ray-curable protective film-forming film.
For example, the illuminance of energy rays during energy ray curing of the energy ray curable protective film-forming film is preferably 120 to 280 mW/cm ² . The amount of energy rays used during curing is preferably 100 to 1000 mJ/cm ² .

<Energy ray curable protective film forming composition (IV)>
As a preferable composition for forming an energy ray curable protective film, for example, an energy ray curable composition for forming a protective film containing the energy ray curable component (a) (IV) (herein simply referred to as " (sometimes abbreviated as "Composition (IV)").

[Energy ray curable component (a)]
The energy ray curable component (a) is a component that is cured by irradiation with energy rays, and provides film-forming properties, flexibility, etc. to the energy ray curable protective film forming film, and forms a hard protective film after curing. It is also an ingredient for forming.
In the energy beam-curable protective film-forming film, the energy beam-curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive.

Examples of the energy ray curable component (a) include a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, and a polymer (a1) having an energy ray curable group and a molecular weight of 100 to 80,000. Compound (a2) is mentioned. The polymer (a1) may be at least partially crosslinked with a crosslinking agent or may not be crosslinked.

The composition (IV) and the energy ray curable protective film forming film may contain only one type of energy ray curable component (a), or may contain 2 or more types, and may contain 2 or more types. If so, the combination and ratio thereof can be arbitrarily selected.

[Polymer (b) without energy ray-curable group]
When the composition (IV) and the energy ray curable protective film forming film contain the compound (a2) as the energy ray curable component (a), the composition (IV) further contains a polymer (b) having no energy ray curable group. It is preferable to also contain. In addition, the composition (IV) and the energy ray curable protective film forming film do not contain the compound (a2) and contain the polymer (a1) and the polymer (b) that does not have an energy ray curable group. Both may be contained.

Examples of the polymer (b) that does not have an energy ray-curable group include the same polymer component (A) listed as a component of the above-mentioned composition (III). However, the polymer (b) does not have an energy ray-curable group.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter sometimes abbreviated as "acrylic polymer (b-1)").

When the polymer (b) has a functional group such as a glycidyl group, a hydroxyl group, a substituted amino group, a carboxy group, or an amino group, the polymer (b) is crosslinked with a crosslinking agent. Good too.

The composition (IV) and the energy ray curable protective film-forming film may contain only one type of polymer (b) having no energy ray curable group, or two or more types. If there are two or more types, their combination and ratio can be selected arbitrarily.

When the composition (IV) contains the compound (a2) and either or both of the polymer (a1) and the polymer (b) which does not have an energy ray-curable group, the composition (IV) In IV), the content of the compound (a2) is 10 to 400 parts by mass based on 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group. The amount is preferably 30 to 350 parts by mass, and more preferably 30 to 350 parts by mass.

Total content of the energy ray curable component (a) and the polymer (b) having no energy ray curable group, relative to the total mass of the energy ray curable protective film forming film, in the energy ray curable protective film forming film. The proportion of is preferably 5 to 90% by mass, more preferably 10 to 80% by mass. When the ratio is within such a range, the energy ray curable protective film forming film has better film forming properties, flexibility, and energy ray curability.

In addition to the energy beam curable component (a), the composition (IV) may contain a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a coloring agent, and a general-purpose additive depending on the purpose. It may contain one or more selected from the group consisting of:

The thermosetting component, filler, coupling agent, crosslinking agent, photoinitiator, coloring agent, and general-purpose additive in composition (IV) are the thermosetting component (B) in composition (III), respectively. ), filler (D), coupling agent (E), crosslinking agent (F), photopolymerization initiator (H), colorant (I), and general-purpose additive (J).
The energy ray-curable protective film-forming film containing these components has the same effects as the thermosetting protective film-forming film containing these components. In particular, since the photopolymerization initiator efficiently advances the energy ray curing reaction, it is preferable that the energy ray curable protective film forming film contains a photopolymerization initiator.

The content of the thermosetting component, filler, coupling agent, crosslinking agent, photopolymerization initiator, coloring agent, and general-purpose additive in composition (IV) may be adjusted as appropriate depending on the purpose, and there are no particular limitations. Not done.

Composition (IV) preferably further contains a solvent because its handling properties are improved by dilution.
Examples of the solvent contained in composition (IV) include the same solvents as in composition (III).
Composition (IV) may contain only one type of solvent, or may contain two or more types.
The content of the solvent in composition (IV) is not particularly limited, and may be appropriately selected depending on the types of components other than the solvent, for example.

<Method for producing energy ray curable protective film forming composition (IV)>
Composition (IV) can be obtained by blending the components for constituting it.
The energy ray-curable composition for forming a protective film can be produced, for example, by the same method as for the composition for forming a thermosetting protective film described above, except that the types of ingredients are different.

◎Non-curable protective film-forming film Preferred non-curing protective film-forming films include, for example, those containing a thermoplastic resin and a filler.

<Non-curable protective film forming composition (V)>
Preferred non-curable protective film-forming compositions include, for example, non-curable protective film-forming composition (V) containing the thermoplastic resin and filler (herein simply referred to as "composition (V)"). )”), etc.

[Thermoplastic resin]
The thermoplastic resin is not particularly limited.
More specifically, examples of the thermoplastic resin include the same ones as the polymer component (A) listed as a component of the above-mentioned composition (III). However, the thermoplastic resin does not have an energy ray-curable group.

The composition (V) and the non-curable protective film-forming film may contain only one type of thermoplastic resin, or may contain two or more types, and when they are two or more types, Combinations and ratios can be selected arbitrarily.

In the non-curable protective film-forming film, the content ratio of the thermoplastic resin to the total mass of the non-curable protective film-forming film is preferably 25 to 75% by mass.

[Filling material]
A non-curable protective film-forming film containing a filler has the same effect as a thermosetting protective film-forming film containing a filler (D).

The filler contained in the composition (V) and the non-curable protective film-forming film includes the same filler (D) contained in the composition (III) and the thermosetting protective film-forming film.

The composition (V) and the non-curable protective film-forming film may contain only one kind of filler, or two or more kinds of fillers, and when they are two or more kinds, a combination thereof and The ratio can be selected arbitrarily.

In the non-curable protective film-forming film, the content ratio of the filler to the total mass of the non-curable protective film-forming film is preferably 15 to 70% by mass. When the ratio is within this range, it becomes easier to adjust the thermal expansion coefficient of the non-curable protective film-forming film and the protective film, as in the case of using composition (III).

In addition to the thermoplastic resin and filler, the composition (V) may contain other components depending on the purpose.
The other components are not particularly limited and can be arbitrarily selected depending on the purpose.
For example, by using the composition (V) containing the thermoplastic resin and a coloring agent, the non-curable protective film-forming film and protective film formed are different from the thermosetting protective film-forming film described above. The same effect as when containing agent (I) is expressed.

In the composition (V), the other components may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof may be determined arbitrarily. You can choose.

The content of the other components in composition (V) may be adjusted as appropriate depending on the purpose and is not particularly limited.

Composition (V) preferably further contains a solvent because its handling properties are improved by dilution.
Examples of the solvent contained in composition (V) include the same solvents as those in composition (III) described above.
Composition (V) may contain only one type of solvent, or may contain two or more types.
The content of the solvent in composition (V) is not particularly limited, and may be appropriately selected depending on, for example, the types of components other than the solvent.

<Method for producing non-curable protective film forming composition (V)>
Composition (V) is obtained by blending the components for constituting this.
The non-curable protective film-forming composition can be produced, for example, in the same manner as the thermosetting protective film-forming composition described above, except that the types of ingredients are different.

<<An example of a preferable protective film forming sheet>>
In the protective film forming sheet, the peeling force of the first release film to the protective film forming film, the peeling force of the second release film to the protective film forming film, and the difference in peeling force between the second release film and the first release film are , are preferably in any of the numerical ranges mentioned above. Such a protective film forming sheet has extremely excellent properties.
As an example of a preferable protective film forming sheet, the difference in peel force between the second release film and the first release film is 30 mN/100 mm or more and less than 200 mN/100 mm, and the peel force of the first release film with respect to the protective film forming film is 20 mN. /100 mm or more, and the peeling force of the second release film to the protective film forming film is 500 mN/100 mm or less.

In the protective film-forming sheet, a region on which the protective film-forming film is not laminated (non-laminated region) of the surface of the first release film on the protective film-forming film side and a protective film-forming film of the second release film There may or may not be inclusions between the side surface and the area where the protective film-forming film is not laminated (non-lamination area), but there are substantially no inclusions. It is preferable. Using such a protective film-forming sheet, the first release film is peeled off from the protective film-forming film (for example, in the first peeling step in the method for manufacturing a workpiece with a protective film described later), and the peeled first release film is When the release film is wound up into a roll, the first release film is prevented from slipping. Similarly, using such a protective film forming sheet, the second release film is peeled off from the protective film forming film or the protective film (for example, the second peeling step in the method for manufacturing a workpiece with a protective film described below). When this peeled second release film is wound up into a roll, the winding shift of the second release film is suppressed. Further, such a protective film forming sheet can be manufactured at a lower cost.

As used herein, "substantially free of inclusions" means that there are no inclusions at all, or even if there are inclusions, the maximum width of the inclusions is less than 5 mm. Here, the maximum width of an inclusion means the maximum length of a line segment connecting two different points on the surface of the inclusion. Thus, for example, the maximum width of a spherical inclusion is the diameter of this sphere.

In the protective film forming sheet, when there are substantially no inclusions between the non-laminated area of the first release film and the non-laminated area of the second release film, the A part of the non-laminated area and a part of the non-laminated area of the second release film may or may not be in contact with each other.

<<Example of protective film forming sheet>>
FIG. 2(a) is a plan view schematically showing an example of the protective film forming sheet of the present embodiment, and FIG. 2(b) is a plan view schematically showing an example of the protective film forming sheet shown in FIG. FIG. 2 is a diagram schematically showing a cross section taken along line II.
In the figures after FIG. 2, the same components as those shown in the already explained figures are given the same reference numerals as in the already explained figures, and detailed explanation thereof will be omitted.

The protective film forming sheet 1 shown here includes a first release film 12, a second release film 13 having a greater peeling force than the first release film 12, and a bond between the first release film 12 and the second release film 13. A protective film forming film 11 is provided. As shown in FIG. 2(a), both the first release film 12 and the second release film 13 are long. FIG. 2A is a plan view of the protective film forming sheet 1 viewed from above on the first release film 12 side.
In the protective film forming sheet 1, two or more protective film forming films 11 are arranged along the longitudinal direction of one first release film 12 and one second release film 13. , two or more protective film forming films 11 are arranged in a line along the longitudinal direction of one first release film 12 and one second release film 13. Here, the reference numeral 11a indicates the surface of the protective film forming film 11 on the first release film 12 side (herein sometimes referred to as "first surface"), and the reference numeral 11b indicates the protective film forming film 11. 11 on the second release film 13 side (herein sometimes referred to as "second surface").
The planar shape of the protective film forming film 11 is entirely circular or approximately circular.
The diameter D ₁₁ of the protective film forming film 11 is 135 mm or more and less than 150 mm, 185 mm or more and less than 200 mm, 285 mm or more and less than 300 mm, or 435 mm or more and less than 450 mm.

The first release film 12 does not substantially have a notch at a position that coincides with the outer periphery 11c of the protective film forming film 11, and the second release film 13 has no notch at the outer periphery of the protective film forming film 11. A notch 139 is provided at a position that coincides with the portion 11c. The depth of the cut 139 is less than 1 μm. The cut 139 has a circular or substantially circular shape when viewed from above in a planar view.

The difference between the peeling force of the second release film 13 to the protective film forming film 11 and the peeling force of the first release film 12 to the protective film forming film 11 is preferably 30 mN/100 mm or more and less than 200 mN/100 mm.
The peel force of the first release film 12 against the protective film forming film 11 is preferably 20 mN/100 mm or more.
The peeling force of the second release film 13 against the protective film forming film 11 is preferably 500 mN/100 mm or less.
When the surface 12b of the first release film 12 on the protective film forming film 11 side and the surface of the stainless steel (SUS) plate are attached, the adhesive force between the first release film 12 and the stainless steel plate is 50 mN. /25 mm, and at least the region 122b on which the protective film forming film 11 is not laminated (non-laminated region) of the surface 12b of the first release film 12 on the protective film forming film 11 side is It is preferable that the adhesive force is less than 50 mN/25 mm, and the entire area (entire surface) of the surface 12b may have the above-mentioned adhesive force (less than 50 mN/25 mm).
When the surface 13a of the second release film 13 on the protective film forming film 11 side is attached to the surface of the stainless steel (SUS) plate, the adhesive force between the second release film 13 and the stainless steel plate is 50 mN. /25 mm, and at least an area 132a on which the protective film forming film 11 is not laminated (non-laminated area) of the surface 13a of the second release film 13 on the protective film forming film 11 side has the above-mentioned attachment. It is preferable to have an adhesive force (less than 50 mN/25 mm), and the entire area (entire surface) of the surface 13a may have the above-mentioned adhesive force (less than 50 mN/25 mm).

In the protective film forming sheet 1, a region 122b on which the protective film forming film 11 is not laminated (non-laminated region) 122b of the surface 12b of the first release film 12 on the protective film forming film 11 side, and a second release film It is preferable that there be substantially no inclusions between the surface 13a of No. 13 on the protective film forming film 11 side and a region 132a on which the protective film forming film 11 is not laminated (non-laminated region). When there are substantially no inclusions between the non-laminated region 122b of the first release film 12 and the non-laminated region 132a of the second release film 13, as shown in FIG. 2(b), The non-laminated area 122b of the first release film 12 and the non-laminated area 132a of the second release film 13 may not be in contact with each other, and as shown in FIG. A part of the non-laminated area 122b and a part of the non-laminated area 132a of the second release film 13 may be in contact with each other. FIG. 3 is a cross-sectional view schematically showing another example of the protective film forming sheet of this embodiment.
Of the surface 12b of the first release film 12 on the protective film forming film 11 side, a region 121b where the protective film forming film 11 is laminated (laminated region) is surrounded by the non-laminated region 122b, and its shape is , is the same as the planar shape of the protective film forming film 11.
Similarly, of the surface 13a of the second release film 13 on the protective film forming film 11 side, a region (laminated region) 131a where the protective film forming film 11 is laminated is surrounded by the non-laminated region 132a, Its shape is the same as the planar shape of the protective film forming film 11.

The thickness T _131a of the part of the second release film 13 where the protective film forming film 11 is laminated (the laminated part, the part corresponding to the laminated region 131a in FIG. 2(b)) and the protective film formation The difference (T _131a - T _132a ) between the thickness T _132a of the region where the film 11 is not laminated (the non-laminated region, the region corresponding to the non-laminated region 132a in FIG. 2(b)) is 10 μm. It is preferably less than -10 μm or more.

<<Other examples of protective film forming sheets>>
The protective film-forming sheet of this embodiment is not limited to the above-mentioned one, and the sheets described so far (for example, FIG. 2(a), FIG. 2(b) , protective film forming sheet shown in FIG. 3), some of the configurations may be changed or deleted, or other configurations may be added.

FIG. 4 is a cross-sectional view schematically showing another example of the protective film forming sheet of this embodiment.
In the protective film forming sheet 2 shown here, the second release film 23 does not substantially have a cut at a position that coincides with the outer peripheral part 11c of the protective film forming film 11, and the first release film 22 has a notch 229 at a position that coincides with the outer peripheral portion 11c of the protective film forming film 11. The protective film forming sheet 2 is the same as the protective film forming sheet 1 except for these points.
The first release film 22 is the same as the first release film 12 except that it has cuts 229, and the cuts 229 that the first release film 22 has are the same as the cuts 139 that the second release film 13 has. It is.
The second release film 23 is the same as the second release film 13 except that it does not substantially have cuts.
In the protective film forming sheet 2, a portion of the surface 22b of the first release film 22 on the protective film forming film 11 side, a part of the area where the protective film forming film 11 is not laminated (non-laminated area), and a second Of the surface 23a of the release film 23 on the protective film forming film 11 side, a part of the area where the protective film forming film 11 is not laminated (non-laminated area) may be in contact with each other.

FIG. 5(a) is a plan view schematically showing still another example of the protective film forming sheet of the present embodiment, and FIG. 5(b) is a plan view schematically showing the protective film forming sheet shown in FIG. 5(a). FIG. 2 is a diagram schematically showing a cross section taken along line III-III of FIG.
The protective film forming sheet 3 shown here further includes a layer between the first release film 12 and the second release film 13 along the two long sides of each of the first release film 12 and the second release film 13. It is the same as the protective film forming sheet 1 except that a strip-shaped protective film forming film 31 is provided near these long sides. In the width direction of the protective film forming sheet 3, the two protective film forming films 31 are provided near both ends of the first release film 12 and the second release film 13. 11 is arranged between these protective film forming films 31.

The protective film forming film 31 is the same as the protective film forming film 11 except for its shape. The protective film forming film 31 can be formed simultaneously with the protective film forming film 11 when manufacturing the protective film forming sheet 3.
The protective film forming film 31 is interposed between the first release film 12 and the second release film 13 in the protective film forming sheet 3, and the distance between the first release film 12 and the second release film 13 is functions as a spacer to maintain the value above a certain value.

Since the protective film-forming sheet 3 includes the protective film-forming film 31, when the protective film-forming sheet 3 is wound up into a roll and then let out from the roll, the first release film and the second release film are removed. The occurrence of curling marks on the protective film forming film 11 is suppressed.

The width of the protective film forming film 31 is preferably 5 to 20 mm.
The thickness of the protective film forming film 31 may be the same as the thickness of the protective film forming film 11.

FIG. 6 is a cross-sectional view schematically showing still another example of the protective film forming sheet of this embodiment.
The protective film forming sheet 4 shown here is provided between the first release film 22 and the second release film 23 and along the two long sides of each of the first release film 22 and the second release film 23. It is the same as the protective film forming sheet 2 except that a strip-shaped protective film forming film 41 is provided near these long sides. In the width direction of the protective film forming sheet 4, the two protective film forming films 41 are provided near both ends of the first release film 22 and the second release film 23, and the two or more protective film forming films 41 are provided near both ends of the first release film 22 and the second release film 23. 11 is arranged between these protective film forming films 41.

The protective film forming film 41 is the same as the protective film forming film 11 except for its shape, and the arrangement of the protective film forming film 41 on the protective film forming sheet 4 is different from that of the protective film forming film 31. This is the same as the arrangement of the forming film 31.
The protective film forming sheet 4 has the same effect as the protective film forming sheet 3.
The protective film forming film 41 is prepared by peeling off the second release film from the protective film forming film or the protective film using such a protective film forming sheet 4 (for example, in the method for manufacturing a workpiece with a protective film described below). 2), the peeled second release film may be removed before being wound up into a roll.

FIG. 7 is a cross-sectional view schematically showing still another example of the protective film forming sheet of this embodiment.
The protective film forming sheet 5 shown here is similar to FIGS. 2(a) and 2( The protection shown in FIG. 4 is the same as the protective film forming sheet 1 shown in b), except that the first release film 12 having no cuts is provided instead of the first release film 22 having the cuts 229. This is the same as the film forming sheet 2.
In the protective film forming sheet 5, of the surface 12b of the first release film 12 on the protective film forming film 11 side, a part of the area where the protective film forming film 11 is not laminated (non-laminated area) and a second Of the surface 23a of the release film 23 on the protective film forming film 11 side, a part of the area where the protective film forming film 11 is not laminated (non-laminated area) may be in contact with each other.

FIG. 8 is a cross-sectional view schematically showing still another example of the protective film forming sheet of this embodiment.
The protective film forming sheet 6 shown here is similar to FIGS. 5A and 5( The protection shown in FIG. 6 is the same as the protective film forming sheet 3 shown in b) except that the first release film 12 having no cuts is provided instead of the first release film 22 having the cuts 229. This is the same as the film forming sheet 4.
The protective film forming film 41 is prepared by peeling off the second release film from the protective film forming film or the protective film using such a protective film forming sheet 6 (for example, in the method for manufacturing a workpiece with a protective film described below). 2), the peeled second release film may be removed before being wound up into a roll.

<<Production method of protective film forming sheet>>
The protective film forming sheet of this embodiment can be manufactured by appropriately combining known protective film forming sheet manufacturing methods.
For example, the protective film forming sheet of the present embodiment includes a first release film or a second release film, a release film for removal, and these (the first release film or the second release film, and the release film for removal). A protective film-forming film provided between the laminate sheets is prepared, and the first release film or the second release film is applied to the laminate sheet from the exposed surface of the release film for removal. A diameter of 135 mm or more and less than 150 mm, 185 mm or more and less than 200 mm, 285 mm or more and less than 300 mm, or 435 mm that passes through the surface of the film on the protective film forming film side and reaches the inside of the first release film or second release film. Two or more circular or approximately circular cuts of less than 450 mm are formed along the longitudinal direction of the laminated sheet, and the protective film forming film and the release film for removal are formed in a first region having a circular or approximately circular planar shape. and a second region other than that, to produce a first intermediate, and in the first intermediate, the second region of the protective film forming film and the release film for removal is divided into the first region film or the second release film, and further remove the first area of the removal release film affixed to the first area of the protective film forming film (by removing the residue). 1 release film or a second release film, and a diameter of 135 mm or more and less than 150 mm, 185 mm or more and less than 200 mm, 285 mm or more and less than 300 mm, or 435 mm or more, provided on one surface of the first release film or the second release film. two or more circular or substantially circular protective film-forming films less than 450 mm, wherein the first release film or the second release film coincides with the outer periphery of the circular or substantially circular protective film-forming film. A second intermediate body having a notch is prepared at the position, and when the second intermediate body is provided with the first release film, a second release film is newly prepared, and the second intermediate body is provided with the first release film. When a second release film is provided, a first release film is newly prepared, and the first release film or second release film side of all the protective film forming films in the second intermediate is It can be manufactured by attaching the newly prepared second release film or first release film to the exposed surface on the opposite side. When or after pasting the newly prepared second release film or first release film, the surface of the first release film on the protective film forming film side and the protective film of the second release film The surface on the forming film side may be brought into contact (bonded together) in a region other than the vicinity of the protective film forming film.
By this manufacturing method (herein sometimes referred to as "manufacturing method (α)"), one of the first release film and the second release film is attached to the outer periphery of the protective film forming film. A protective film forming sheet having notches at matching positions (for example, protective film forming sheet 1 shown in FIGS. 2(a), 2(b), and 3, and protective film forming sheet 2 shown in FIG. 4) can be manufactured.
Further, in the present manufacturing method (manufacturing method (α)), when producing the second intermediate, cuts are further formed in the laminated sheet so as to form a protective film forming film as the spacer. In some cases, a protective film forming sheet including a protective film forming film as the spacer (for example, the protective film forming sheet 3 shown in FIGS. 5(a) and 5(b), the protective film forming sheet 3 shown in FIG. Sheet 4) can be manufactured.

Further, for example, in the protective film forming sheet of the present embodiment, two or more protective film forming films each having a circular or substantially circular planar shape can be formed along the longitudinal direction of the first release film or the second release film. Masking is performed by forming a mask on one surface of the first release film or the second release film, and on the one surface of the first release film or the second release film after the masking, forming a layer of a protective film-forming composition for forming the protective film-forming film; forming the protective film-forming film from the layer of the protective film-forming composition; and forming the first release film or the second release film. By removing the mask and the protective film forming film on the mask from the one surface of the film, a layer having a diameter of 135 mm or more is formed on the one surface of the first release film or the second release film. Two or more circular or substantially circular protective film-forming films with a diameter of less than 150 mm, 185 mm or more and less than 200 mm, 285 mm or more and less than 300 mm, or 435 mm or more and less than 450 mm are formed, and the protective film-forming film is provided on the first release film. If the protective film-forming film is provided on the second release film, a new first release film is prepared, and all It can be manufactured by attaching the newly prepared second release film or first release film to the exposed surface of the protective film forming film opposite to the first release film or second release film side. When or after pasting the newly prepared second release film or first release film, the surface of the first release film on the protective film forming film side and the protective film of the second release film The surface on the forming film side may be brought into contact (bonded together) in a region other than the vicinity of the protective film forming film.
According to this manufacturing method (herein sometimes referred to as "manufacturing method (β)"), both the first release film and the second release film coincide with the outer periphery of the protective film forming film. This method is suitable as a method for producing a protective film forming sheet (for example, the protective film forming sheet 5 shown in FIG. 7) having substantially no notches at any position.
Further, in the manufacturing method (β), by forming the above mask so as to form a protective film forming film as the spacer in addition to the protective film forming film having a circular or substantially circular planar shape, A protective film forming sheet (for example, the protective film forming sheet 6 shown in FIG. 8) including a protective film forming film as the spacer can be manufactured.
In the manufacturing method (β), the protective film-forming film and the protective film-forming film as the spacer are formed on the one surface of the first release film or the second release film after masking. When forming a layer of the composition for forming a protective film, the composition for forming a protective film may be coated on the one surface.

For example, the protective film forming sheet of the present embodiment may have a planar shape formed on one surface of the first release film or the second release film along the longitudinal direction of the first release film or the second release film. Form a layer of a protective film-forming composition for forming a protective film-forming film having two or more circular or substantially circular shapes, and from the layer of the protective film-forming composition, a layer having a diameter of 135 mm or more and less than 150 mm, 185 mm. Two or more circular or nearly circular protective film-forming films with a length of at least 200 mm, at least 285 mm and less than 300 mm, or at least 435 mm and less than 450 mm are formed, and the protective film-forming film is provided on the first release film. In this case, a second release film is newly prepared, and if the protective film forming film is provided on the second release film, a first release film is newly prepared and all of the protective film forming It can be manufactured by attaching the newly prepared second release film or first release film to the exposed surface of the film opposite to the first release film or second release film side. When or after pasting the newly prepared second release film or first release film, the surface of the first release film on the protective film forming film side and the protective film of the second release film The surface on the forming film side may be brought into contact (bonded together) in a region other than the vicinity of the protective film forming film.
According to this manufacturing method (herein sometimes referred to as "manufacturing method (γ)"), both the first release film and the second release film coincide with the outer periphery of the protective film forming film. This method is suitable as a method for producing a protective film forming sheet (for example, the protective film forming sheet 5 shown in FIG. 7) having substantially no notches at any position.
In addition, in the manufacturing method (γ), in addition to the protective film-forming film having a circular or substantially circular planar shape, a layer of a protective film-forming composition for forming the protective film-forming film as the spacer is further formed. By forming a protective film-forming film as a spacer from the layer of the protective film-forming composition, a protective film-forming sheet (for example, as shown in FIG. 8 A protective film forming sheet 6) can be manufactured.
In the manufacturing method (γ), a protective film forming film for forming the protective film forming film and the protective film forming film as the spacer on one surface of the first release film or the second release film. When forming a layer of the composition, the composition for forming a protective film may be printed on the one surface by a printing method such as a screen printing method.

◇Production method for workpieces with protective film (how to use protective film forming sheet)
The protective film forming sheet can be used for manufacturing a workpiece with a protective film.
In the method for manufacturing a workpiece with a protective film according to an embodiment of the present invention, the workpiece with a protective film includes a workpiece and a protective film provided on one surface of the workpiece. The workpiece is obtained by processing a workpiece, the planar shape of the workpiece is circular, and the diameter of the workpiece is 6 inches, 8 inches, 12 inches, or 18 inches, The protective film is formed from the protective film forming film in the protective film forming sheet, and when the diameter of the workpiece is 6 inches, the diameter of the protective film forming film is 135 mm or more and 150 mm. and when the diameter of the workpiece is 8 inches, the diameter of the protective film forming film is 185 mm or more and less than 200 mm, and when the diameter of the workpiece is 12 inches, the protective film forming film has a diameter of 285 mm or more and less than 300 mm, and the workpiece has a diameter of 18 inches, the diameter of the protective film-forming film is 435 mm or more and less than 450 mm, and the protective film-forming film is curable. is a cured product of the protective film-forming film, and when the protective film-forming film is non-curable, the protective film-forming film after being attached to any part of the workpiece. is the protective film, and the method for manufacturing a workpiece with a protective film includes: a first peeling step of peeling off the first release film from the protective film forming film in the protective film forming sheet; After the peeling step, the surface of the protective film forming film on the side where the first peeling film was provided is removed from one side of the work without causing the outer peripheral part of the protective film forming film to protrude from the outer peripheral part of the workpiece. a first laminate step of producing a first laminate in which the protective film-forming film or the protective film is provided on the workpiece by pasting the first laminate onto the surface of the workpiece; a second peeling step of peeling the second release film from the protective film-forming film or the protective film inside, and after the second peeling step, the protective film-forming film or the second release film of the protective film is removed. By pasting a processing sheet for processing the workpiece on the side where the workpiece was provided, the processing sheet, the protective film forming film or the protective film, and the workpiece are processed in this order. a second affixing step of producing a second laminate configured by laminating in the thickness direction; and a processing step of producing the workpiece by processing the workpiece after the second affixing step; After the second pasting step, a cutting step of cutting the protective film forming film or the protective film is provided, and when the protective film forming film is curable, the second peeling step further includes a cutting step of cutting the protective film forming film or the protective film. Later, the method includes a curing step of forming the protective film by curing the protective film forming film.

In each step after the first pasting step, which one of the protective film forming film and the protective film is handled is determined at the timing of forming the protective film. When the protective film-forming film is non-curable, the protective film is handled in any step after the first application step. When the protective film-forming film is curable, it is the protective film-forming film that is handled before the curing process, and the protective film is handled after the curing process.

When the workpiece is a semiconductor wafer, in the method for manufacturing a workpiece with a protective film according to an embodiment of the present invention, that is, the method for manufacturing a semiconductor chip with a protective film, the semiconductor chip with a protective film includes a semiconductor chip, a protective film provided on the back surface of a semiconductor chip, the semiconductor chip is obtained by processing (dividing) a semiconductor wafer, the planar shape of the semiconductor wafer is circular, and the semiconductor wafer has a The diameter of the semiconductor wafer is 6 inches, 8 inches, 12 inches, or 18 inches, the protective film is formed from the protective film forming film in the protective film forming sheet, and the diameter of the semiconductor wafer is When the diameter of the protective film forming film is 6 inches, the diameter of the protective film forming film is 135 mm or more and less than 150 mm, and when the diameter of the semiconductor wafer is 8 inches, the diameter of the protective film forming film is 185 mm or more and less than 200 mm. When the diameter of the semiconductor wafer is 12 inches, the diameter of the protective film forming film is 285 mm or more and less than 300 mm, and when the diameter of the semiconductor wafer is 18 inches, the protective film forming film is has a diameter of 435 mm or more and less than 450 mm, and the protective film-forming film is curable, the cured product of the protective film-forming film is the protective film, and the protective film-forming film is non-curable. In this case, the protective film forming film attached to the back surface of the semiconductor wafer is the protective film, and the method for manufacturing a semiconductor chip with a protective film includes forming the protective film in the protective film forming sheet. A first peeling step of peeling the first release film from the film, and after the first peeling step, the protective film forming film is removed without causing the outer peripheral portion of the protective film forming film to protrude from the outer peripheral portion of the semiconductor wafer. A first laminate in which the protective film forming film or the protective film is provided on the semiconductor wafer by attaching the side on which the first release film was provided to one surface of the semiconductor wafer. a second peeling step of peeling the second release film from the protective film forming film or the protective film in the first laminate after the first pasting step; After the second peeling step, a processing sheet for processing the semiconductor wafer is attached to the surface of the protective film forming film or the surface of the protective film on which the second release film was provided. and a second pasting step of producing a second laminate in which the protective film forming film or the protective film and the semiconductor wafer are laminated in this order in the thickness direction; A processing step of fabricating the semiconductor chip by processing (dividing) the semiconductor wafer after the pasting step, and a cutting step of cutting the protective film forming film or the protective film after the second pasting step. , and when the protective film-forming film is curable, a curing step of forming the protective film by curing the protective film-forming film after the second peeling step; A method for manufacturing a semiconductor chip with a protective film is mentioned.

According to the manufacturing method, when applying the protective film-forming film to the workpiece (in the first pasting step), the protective film-forming film can be used to attach the workpiece to the workpiece without reducing the manufacturing efficiency of the workpiece with the protective film. Contamination can be suppressed, there is no need to punch out the first release film or the second release film when using the protective film forming sheet, and the used first release film or second release film can be reused.

The manufacturing method includes a manufacturing method that includes the curing step (herein sometimes referred to as "manufacturing method (1)") and a manufacturing method that does not include the curing step (hereinafter referred to as "manufacturing method (1)"). (sometimes referred to as "manufacturing method (2)").
Hereinafter, these manufacturing methods will be explained one by one.

<<Manufacturing method (1)>>
In the manufacturing method (1), the workpiece with a protective film includes a workpiece and a protective film provided on one surface of the workpiece, and the workpiece has a protective film attached to the workpiece. The planar shape of the workpiece is circular, the diameter of the workpiece is 6 inches, 8 inches, 12 inches, or 18 inches, and the protective film is obtained by processing the protective film forming sheet. When the diameter of the workpiece is 6 inches, the diameter of the protective film formation film is 135 mm or more and less than 150 mm, and the diameter of the workpiece is 8 inches. In this case, the diameter of the protective film forming film is 185 mm or more and less than 200 mm, and when the diameter of the workpiece is 12 inches, the diameter of the protective film forming film is 285 mm or more and less than 300 mm, and the When the diameter of the workpiece is 18 inches, the diameter of the protective film forming film is 435 mm or more and less than 450 mm, and the protective film forming film is curable, so that the cured product of the protective film forming film is curable. The method for producing a workpiece with a protective film includes a first peeling step of peeling off the first release film from the protective film forming film in the protective film forming sheet; Afterwards, the surface of the protective film-forming film on the side where the first release film was provided is placed on one surface of the workpiece without causing the outer peripheral part of the protective film-forming film to protrude from the outer peripheral part of the workpiece. A first pasting step of producing a first laminate in which the protective film forming film is provided on the workpiece by pasting, and after the first pasting step, the protective film forming film in the first laminate is pasted. a second peeling step of peeling the second release film from the workpiece, and after the second peeling step, the protective film forming film or the surface of the protective film on the side where the second release film was provided, the workpiece. By pasting a processing sheet for processing, the processing sheet, the protective film forming film or the protective film, and the workpiece are laminated in this order in the thickness direction. 2. A second attaching step of producing a laminate; a processing step of producing the workpiece by processing the workpiece after the second attaching step; and a processing step of producing the workpiece after the second attaching step; The method includes a cutting step of cutting the formed film or the protective film, and a curing step of forming the protective film by curing the protective film forming film after the second peeling step.

When the work is a semiconductor wafer, in the manufacturing method (1), the semiconductor chip with a protective film includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip, and the semiconductor chip includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip. The chip is obtained by processing (dividing) a semiconductor wafer, the planar shape of the semiconductor wafer is circular, the diameter of the semiconductor wafer is 6 inches, 8 inches, 12 inches, or 18 inches; The protective film is formed from the protective film forming film in the protective film forming sheet, and when the diameter of the semiconductor wafer is 6 inches, the diameter of the protective film forming film is 135 mm or more and 150 mm. and when the diameter of the semiconductor wafer is 8 inches, the diameter of the protective film forming film is 185 mm or more and less than 200 mm, and when the diameter of the semiconductor wafer is 12 inches, the protective film is When the diameter of the forming film is 285 mm or more and less than 300 mm, and the diameter of the semiconductor wafer is 18 inches, the diameter of the protective film forming film is 435 mm or more and less than 450 mm, and the protective film forming film is curable. Therefore, the cured product of the protective film forming film is the protective film, and the method for manufacturing a semiconductor chip with a protective film includes peeling the first release film from the protective film forming film in the protective film forming sheet. and after the first peeling step, the first peeling film of the protective film forming film is provided without causing the outer peripheral part of the protective film forming film to protrude from the outer peripheral part of the semiconductor wafer. a first attaching step of producing a first laminate in which the protective film-forming film is provided on the semiconductor wafer by attaching the side that had previously been attached to the back surface of the semiconductor wafer; Later, a second peeling step of peeling off the second release film from the protective film-forming film in the first laminate; and after the second peeling step, the protective film-forming film or the second release film of the protective film is removed. By pasting a processing sheet for processing the semiconductor wafer on the side where the release film was provided, the processing sheet, the protective film forming film or the protective film, and the semiconductor wafer are separated. In this order, the semiconductor wafer is processed (divided) by a second adhesion step of producing a second laminate configured by laminating these layers in the thickness direction, and after the second adhesion step, the semiconductor wafer is processed (divided). By curing the protective film forming film after the processing step of producing a chip, the cutting step of cutting the protective film forming film or the protective film after the second pasting step, and the second peeling step. , a curing step of forming the protective film.

The order in which the machining process and cutting process are performed can be arbitrarily selected depending on the purpose; the machining process may be performed before the cutting process, the machining process and the cutting process may be performed at the same time, or the cutting process may be performed simultaneously. After that, the processing step may be performed.
In this embodiment, if the processing of the workpiece and the cutting of the protective film forming film or the protective film are performed continuously by the same operation without interruption, regardless of the order, the processing step and the cutting step are considered to have taken place at the same time.

Both the processing step and the cutting step can be performed by known methods depending on the order in which they are performed.

When the workpiece is a semiconductor wafer and the cutting process is performed after the processing (dividing) process, the semiconductor wafer is divided (in other words, into pieces) by stealth dicing (registered trademark) or laser dicing, etc. It can be carried out.
Stealth dicing (registered trademark) is a method as follows. That is, first, a location to be divided is set inside the semiconductor wafer, and a modified layer is formed inside the semiconductor wafer by irradiating laser light with this location as a focal point. . Unlike other parts of the semiconductor wafer, the modified layer of the semiconductor wafer is altered by the laser light irradiation, and its strength is weakened. Therefore, when force is applied to the semiconductor wafer, cracks extending in the direction of both surfaces of the semiconductor wafer are generated in the modified layer inside the semiconductor wafer, which becomes a starting point for division (cutting) of the semiconductor wafer. Next, force is applied to the semiconductor wafer to divide the semiconductor wafer at the modified layer portions, thereby producing semiconductor chips.

When the workpiece is a semiconductor wafer and the cutting process is performed after the processing (dividing) process, the protective film forming film or the protective film is cut by, for example, cutting the protective film forming film or the protective film onto the semiconductor chip. This can be done by so-called expanding, which involves pulling in a direction parallel to the surface to which it is attached. The expanded protective film forming film or protective film is cut along the outer periphery of the semiconductor chip. Such expanding cutting is preferably carried out at a low temperature such as -20 to 5°C.

When the workpiece is a semiconductor wafer and the processing (dividing) process and cutting process are performed at the same time, each dicing method may be used, such as blade dicing using a blade, laser dicing using laser irradiation, or water dicing using spraying water containing an abrasive. , it is possible to simultaneously divide the semiconductor wafer and cut the protective film forming film or the protective film.
In addition, a semiconductor wafer on which a modified layer has been formed by stealth dicing (registered trademark) and which has not been divided and a protective film forming film or a protective film are expanded in the same manner as above. It is also possible to divide the wafer and cut the protective film forming film or protective film at the same time.

If the workpiece is a semiconductor wafer and the cutting process is followed by the processing (dividing) process, the same method as above for each dicing process can be used to remove the protective film forming film or protective film without dividing the semiconductor wafer. can be cut, and the semiconductor wafer can then be divided by braking.

9 to 10 are cross-sectional views schematically illustrating an example of the manufacturing method (1) when the workpiece is a semiconductor wafer. Here, a manufacturing method using the protective film forming sheet 1 shown in FIGS. 2(a) and 2(b) will be described.

<First peeling step>
In the first peeling step of manufacturing method (1), as shown in FIG. 9(a), the first peeling film 12 is peeled from the protective film forming film 11 in the protective film forming sheet 1.
The peeling speed at this time is preferably 5 to 100 mm/s.

In the protective film-forming sheet 1, the first release film 12 has substantially no notches at a position that coincides with the outer peripheral portion 11c of the protective film-forming film 11. Since the notch formed in the release film is usually formed when the protective film forming film is cut, the first release film 12 has the notch formed at a position that coincides with the outer peripheral portion 11c of the protective film forming film 11. If there is substantially no cut, there is also substantially no cut in other areas. Such a first release film 12 is suitable for reuse after being removed from the protective film forming film 11. Furthermore, in the first release film 12 that does not substantially have cuts, the problem of a residual image of a portion of the protective film forming film at the cut site is suppressed. Furthermore, in the protective film forming sheet 1, since the protective film forming film 11 has already been punched into the desired shape, during the use of the protective film forming sheet 1, that is, until the first peeling step is performed. Furthermore, both the punching of the protective film forming film and the accompanying punching of the first release film 12 and the second release film 13 are unnecessary. Therefore, the interior of the apparatus is not contaminated by cutting debris generated during processing of the first release film 12 and the second release film 13.

<First pasting process>
After the first peeling step of manufacturing method (1), in the first pasting step, as shown in FIG. A protective film is formed on the semiconductor wafer 9 by attaching the surface (first surface) 11a of the protective film forming film 11 on the side where the first release film 12 was provided to the back surface 9b of the semiconductor wafer 9 without causing any damage. A first laminate 101 provided with a film 11 is produced. A plurality of protruding electrodes 91 are provided on the circuit surface 9a of the semiconductor wafer 9.

The planar shape of the semiconductor wafer 9 (the shape of the circuit surface 9a and the back surface 9b) is circular, and the planar shape of the protective film forming film 11 (the shape of the first surface 11a and the second surface 11b) is circular or approximately circular. be.
The diameter D ₉ of the semiconductor wafer 9 is 6 inches, 8 inches, 12 inches, or 18 inches, and when the diameter D ₉ of the semiconductor wafer 9 is 6 inches, the diameter D ₁₁ of the protective film forming film 11 is When the diameter D ₉ of the semiconductor wafer 9 is 8 inches, the diameter D ₁₁ of the protective film forming film 11 is 185 mm or more and less than 200 mm, and the diameter D ₉ of the semiconductor wafer 9 is 12 inches. In this case, the diameter D ₁₁ of the protective film forming film 11 is 285 mm or more and less than 300 mm, and when the diameter D ₉ of the semiconductor wafer 9 is 18 inches, the diameter D ₁₁ of the protective film forming film 11 is 435 mm. The length is at least 450 mm. That is, the cross section of the semiconductor wafer 9 in FIG. 9(b) includes the center of the semiconductor wafer 9, and the cross section of the protective film forming film 11 includes the center of gravity of the protective film forming film 11.

In the first pasting process, by D ₉ and D ₁₁ satisfying the above relationship, the protective film forming film 11 can be attached to the semiconductor wafer 9 without causing the outer peripheral part 11c of the protective film forming film 11 to protrude from the outer peripheral part 9c of the semiconductor wafer 9. Since it can be easily attached to the wafer 9, contamination of the semiconductor wafer 9 by the protective film forming film 11 can be suppressed. Furthermore, since D ₁₁ is not excessively small, the usage efficiency of the semiconductor wafer 9 is increased, and a decrease in the manufacturing efficiency of the workpiece with a protective film is suppressed.

In the first attachment step, the attachment speed of the protective film forming film 11 to the semiconductor wafer 9 is preferably 5 to 100 mm/s, and the attachment pressure is preferably 0.15 to 0.6 MPa.

In the first attachment step, the protective film forming film 11 may be softened by heating and then attached to the semiconductor wafer 9.

The back surface 9b of the semiconductor wafer 9 may be ground in order to have a desired thickness. That is, the back surface 9b of the semiconductor wafer 9 may be a ground surface.

<Second peeling process>
After the first pasting step of manufacturing method (1), in the second peeling step, the second peeling film 13 is removed from the protective film forming film 11 in the first laminate 101, as shown in FIG. 9(c). Peel off.

<Curing process>
After the second peeling step of manufacturing method (1), in the curing step, as shown in FIG. 9(d), the protective film forming film 11 is hardened to form a protective film 11'. The curing conditions at this time are as described above.
In FIG. 9(d), 11a' indicates the first surface of the protective film 11', 11b' indicates the second surface of the protective film 11', and 11c' indicates the outer periphery of the protective film 11'. They correspond to the first surface 11a of the protective film-forming film 11, the second surface 11b of the protective film-forming film 11, and the outer peripheral portion 11c of the protective film-forming film 11, respectively. In FIG. 9(d), the first laminate in which the protective film forming film 11 is the protective film 11' is newly designated with the reference numeral 101', and in this specification, this is also referred to as the "first laminate". 1 laminate.

<Second pasting process>
After the second peeling step (here, curing step) of manufacturing method (1), in the second pasting step, as shown in FIG. 10(a), the protective film 11' in the first laminate 101' is removed. A dicing sheet 8, which is a processing sheet for processing the semiconductor wafer 9, is attached to the second surface (here, the exposed surface) 11b'. As a result, a second laminate 102 is manufactured in which the dicing sheet 8, the protective film 11', and the semiconductor wafer 9 are laminated in this order in the thickness direction.

Examples of the dicing sheet 8 include a known dicing sheet that includes a base material 81 and an adhesive layer 82 provided on one surface of the base material 81. The dicing sheet 8 is attached to the protective film 11' on one surface 8a (here, the surface 82a of the adhesive layer 82 on the side opposite to the base material 81 side).
However, the dicing sheet to be used is not limited to this, and may be a dicing sheet that does not include the base material 81 and the adhesive layer 82.

<Processing process, cutting process>
After the second pasting step of manufacturing method (1), in the processing step, as shown in FIG. 10(b), the semiconductor wafer 9 is processed (divided) to produce semiconductor chips 90, In the process, the protective film 11' is cut. In FIG. 10(b), the protective film 11' after cutting is newly designated by the reference numeral 110'. Note that in this specification, the "protective film after cutting" may be simply referred to as "protective film." In FIG. 10B, 90a indicates the circuit surface of the semiconductor chip 90, 90b indicates the back surface of the semiconductor chip 90, 110a' indicates the first surface of the protective film 110' after cutting, and 110b ' indicates the second surface of the protective film 110' after cutting; the circuit surface 9a of the semiconductor wafer 9, the back surface 9b of the semiconductor wafer 9, the first surface 11a' of the protective film 11', and the protective film 11', respectively. It corresponds to the second surface 11b' of.

As explained above, the order in which the processing steps and cutting steps are performed is not limited.
The method of performing the processing step and the cutting step is as described above.

As described above, the target workpiece with a protective film, which is configured to include a semiconductor chip 90 as a workpiece and a protective film 110' provided on one surface (back surface 90b) of the semiconductor chip 90, can be processed. A plurality of semiconductor chips 109 with protective films are obtained. These plurality of semiconductor chips 109 with a protective film are all aligned on one dicing sheet 8, and these semiconductor chips 109 with a protective film and the dicing sheet 8 form a group of semiconductor chips 103 with a protective film. It consists of

Thereafter, the semiconductor chip 109 with a protective film was separated from the dicing sheet 8 and picked up by a known method, and the semiconductor chip with a protective film was mounted using the picked up semiconductor chip 109 with a protective film by a known method. Semiconductor devices can be manufactured.

<Other processes>
Manufacturing method (1) does not fall under any of the first peeling process, first pasting process, second peeling process, second pasting process, processing process, cutting process, and curing process. The process may include the following steps.
The types of the other steps and the timing at which they are performed can be arbitrarily selected depending on the purpose and are not particularly limited.

In the other step, for example, a laser beam is applied to the second surface 11b of the protective film forming film 11, the second surface 11b' of the protective film 11', or the second surface 110b' of the protective film 110' after cutting. Examples include a printing step (not shown) of printing on the protective film forming film 11, the protective film 11', or the cut protective film 110' by irradiating light.
In this embodiment, the timing of performing the printing process is not particularly limited.

<Timing to perform the curing process>
Up to this point, we have explained the case where the curing process is performed between the second peeling process and the second pasting process, but the curing process can be performed at any timing as long as it is after the second peeling process. good. For example, the curing step may be performed between the second pasting step and the processing step, between the second pasting step and the cutting step, between the working step and the cutting step, or after the cutting step. However, when performing the printing process, it may be performed either between the printing process and the previous process, or between the printing process and the subsequent process.

<<Manufacturing method (2)>>
In the manufacturing method (2), the workpiece with a protective film includes a workpiece and a protective film provided on one surface of the workpiece, and the workpiece has a protective film attached to the workpiece. The planar shape of the workpiece is circular, the diameter of the workpiece is 6 inches, 8 inches, 12 inches, or 18 inches, and the protective film is obtained by processing the protective film forming sheet. When the diameter of the workpiece is 6 inches, the diameter of the protective film formation film is 135 mm or more and less than 150 mm, and the diameter of the workpiece is 8 inches. In this case, the diameter of the protective film forming film is 185 mm or more and less than 200 mm, and when the diameter of the workpiece is 12 inches, the diameter of the protective film forming film is 285 mm or more and less than 300 mm, and the When the diameter of the workpiece is 18 inches, the diameter of the protective film-forming film is 435 mm or more and less than 450 mm, and the protective film-forming film is non-curable, so that it cannot be attached to any part of the workpiece. The protective film-forming film after the protective film is the protective film, and the method for producing a workpiece with a protective film includes the step of peeling off the first release film from the protective film-forming film in the protective film-forming sheet. 1 peeling step, and after the first peeling step, the side of the protective film forming film where the first peeling film was provided without causing the outer peripheral part of the protective film forming film to protrude from the outer peripheral part of the workpiece. a first attaching step of producing a first laminate in which the protective film is provided on the workpiece by attaching the surface of the workpiece to one side of the workpiece; and after the first attaching step, the first A second peeling step of peeling off the second release film from the protective film in the laminate; and after the second peeling step, the second release film is applied to the surface of the protective film on the side where the second release film was provided. By pasting a processing sheet for processing the workpiece, a second laminate is produced in which the processing sheet, the protective film, and the workpiece are laminated in this order in their thickness direction. a second pasting step of fabricating the workpiece by processing the workpiece after the second pasting step, and a cutting step of cutting the protective film after the second pasting step. and has.

Manufacturing method (2) is the same as manufacturing method (1), regardless of the type of workpiece, except that it does not include the curing step and the protective film forming film after being affixed to the workpiece is used as a protective film as it is. It is.

When the work is a semiconductor wafer, in the manufacturing method (2), the semiconductor chip with a protective film includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip, and the semiconductor chip includes a semiconductor chip and a protective film provided on the back surface of the semiconductor chip. The chip is obtained by processing (dividing) a semiconductor wafer, the planar shape of the semiconductor wafer is circular, the diameter of the semiconductor wafer is 6 inches, 8 inches, 12 inches, or 18 inches; The protective film is formed from the protective film forming film in the protective film forming sheet, and when the diameter of the semiconductor wafer is 6 inches, the diameter of the protective film forming film is 135 mm or more and 150 mm. and when the diameter of the semiconductor wafer is 8 inches, the diameter of the protective film forming film is 185 mm or more and less than 200 mm, and when the diameter of the semiconductor wafer is 12 inches, the protective film is When the diameter of the forming film is 285 mm or more and less than 300 mm, and the diameter of the semiconductor wafer is 18 inches, the diameter of the protective film forming film is 435 mm or more and less than 450 mm, and the protective film forming film is non-curable. Therefore, the protective film forming film after being attached to the back surface of the semiconductor wafer is the protective film, and the method for manufacturing the semiconductor chip with a protective film includes forming the protective film in the protective film forming sheet. A first peeling step of peeling the first release film from the film, and after the first peeling step, the protective film forming film is removed without causing the outer peripheral portion of the protective film forming film to protrude from the outer peripheral portion of the semiconductor wafer. a first attaching step of producing a first laminate in which the protective film is provided on the semiconductor wafer by attaching the side on which the first release film was provided to the back surface of the semiconductor wafer; , a second peeling step of peeling the second release film from the protective film in the first laminate after the first pasting step; and a second peeling of the protective film after the second peeling step. By attaching a processing sheet for processing the semiconductor wafer to the side on which the film was provided, the processing sheet, the protective film, and the semiconductor wafer are arranged in this order to reduce their thickness. a second adhering step of producing a second laminate configured by laminating in the direction; and a processing step of producing the semiconductor chips by processing (dividing) the semiconductor wafer after the second adhering step. , a cutting step of cutting the protective film after the second pasting step.

11 and 12 are cross-sectional views schematically illustrating an example of the manufacturing method (2) when the workpiece is a semiconductor wafer. Here, a manufacturing method using the protective film forming sheet 1 shown in FIGS. 2(a) and 2(b) will be described.

<First peeling step>
The first peeling step of manufacturing method (2) is the same as the first peeling step of manufacturing method (1), as shown in FIG. 11(a). Therefore, in the first peeling step of manufacturing method (2), the same effect as in the first peeling step of manufacturing method (1) can be obtained.

<First pasting process>
After the first peeling step of manufacturing method (2), in the first pasting step, the protective film forming film 11 is removed without causing the outer peripheral portion 11c of the protective film forming film 11 to protrude from the outer peripheral portion 9c of the semiconductor wafer 9. By attaching the surface (first surface) 11a on which the first release film 12 was provided to the back surface 9b of the semiconductor wafer 9, the protective film 11 is attached to the semiconductor wafer 9 as shown in FIG. 11(b). A first laminate 101' provided with ' is produced.
The first affixing step of manufacturing method (2) is the same as the first affixing step of manufacturing method (1), except that the protective film forming film 11 after being affixed to the semiconductor wafer 9 is treated as the protective film 11'. . In order to handle the protective film forming film 11 as a protective film 11' at this stage, the first laminate is given the reference numeral 101' instead of 101.
In the first pasting step of manufacturing method (2), the same effect as in the first pasting step of manufacturing method (1) can be obtained.

<Second peeling process>
After the first pasting step of manufacturing method (2), in the second peeling step, the second peeling film 13 is removed from the protective film 11' in the first laminate 101', as shown in FIG. 11(c). Peel off.

<Second pasting process>
After the second peeling step of manufacturing method (2), in the second pasting step, as shown in FIG. 12(a), the second surface (here, A dicing sheet 8, which is a processing sheet for processing the semiconductor wafer 9, is attached to the exposed surface (11b'). As a result, a second laminate 102 is manufactured in which the dicing sheet 8, the protective film 11', and the semiconductor wafer 9 are laminated in this order in the thickness direction.

<Processing process, cutting process>
After the second pasting step of manufacturing method (2), in the processing step, as shown in FIG. 12(b), semiconductor chips 90 are fabricated by processing (dividing) the semiconductor wafer 9, and In the process, the protective film 11' is cut.

As described above, the target workpiece with a protective film, which is configured to include a semiconductor chip 90 as a workpiece and a protective film 110' provided on one surface (back surface 90b) of the semiconductor chip 90, can be processed. A plurality of semiconductor chips 109 with protective films are obtained. These plurality of semiconductor chips 109 with a protective film are all aligned on one dicing sheet 8, and these semiconductor chips 109 with a protective film and the dicing sheet 8 form a group of semiconductor chips 103 with a protective film. It consists of

Thereafter, by a known method, the semiconductor chip 109 with a protective film is separated from the dicing sheet 8 and picked up in the same manner as in manufacturing method (1), and the picked up semiconductor chip 109 with a protective film is used to perform a known method. A semiconductor device can be manufactured using the method.

<Other processes>
Manufacturing method (2), as in manufacturing method (1), includes a first peeling step, a first pasting step, a second peeling step, a second pasting step, a processing step, a cutting step, It may also include other steps that do not fall under any of the above.
The types of the other steps and the timing at which they are performed can be arbitrarily selected depending on the purpose and are not particularly limited. Examples of the other steps include the same printing step as in manufacturing method (1).

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

<Resin manufacturing raw materials>
The official names of the raw materials for resin production, which are abbreviated in the examples and comparative examples, are shown below.
BA: n-butyl acrylate MA: methyl acrylate GMA: glycidyl methacrylate HEA: 2-hydroxyethyl acrylate

<Raw materials for producing the composition for forming a protective film>
The raw materials used for producing the composition for forming a protective film are shown below.
[Polymer component (A)]
(A)-1: Acrylic resin (weight average molecular weight 400,000, glass transition temperature -1°C).
[Epoxy resin (B1)]
(B1)-1: Liquid bisphenol A type epoxy resin (“jER828” manufactured by Mitsubishi Chemical Corporation, molecule 370, epoxy equivalent 184 to 194 g/eq)
(B1)-2: Dicyclopentadiene type epoxy resin (“Epiclon HP-7200” manufactured by DIC, softening point 56-66°C, epoxy equivalent 254-264 g/eq)
[Thermosetting agent (B2)]
(B2)-1: Dicyandiamide (“DICY7” manufactured by Mitsubishi Chemical Corporation, average particle size 3 μm, maximum particle size 25 μm)
[Curing accelerator (C)]
(C)-1:2-phenyl-4,5-dihydroxymethylimidazole (“Curezol (registered trademark) 2PHZ-PW” manufactured by Shikoku Kasei Kogyo Co., Ltd.)
[Filler (D)]
(D)-1: Silica filler (“SC2050MB” manufactured by Admatex, spherical silica filler surface modified with an epoxy compound, average particle size 0.5 μm, maximum particle size 2.0 μm)
[Coupling agent (E)]
(E)-1:3-glycidoxypropyltrimethoxysilane (silane coupling agent, “KBM403” manufactured by Shin-Etsu Silicone Co., Ltd., molecular weight 236.3)
[Colorant (I)]
(I)-1: Carbon black (“MA600” manufactured by Mitsubishi Chemical Corporation, average particle size 20 nm)

[Example 1]
<<Manufacture of protective film forming sheet>>
<Production of protective film forming composition (III)>
Polymer component (A)-1 (9.22 parts by mass), epoxy resin (B1)-1 (11.82 parts by mass), epoxy resin (B1)-2 (3.7 parts by mass), thermosetting agent ( B2)-1 (0.22 parts by mass), curing accelerator (C)-1 (0.22 parts by mass), filler (D)-1 (73.6 parts by mass), coupling agent (E)- 1 (0.22 parts by mass) and colorant (I)-1 (1 part by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23°C, so that the total concentration of all components other than the solvent was 67. A thermosetting protective film-forming composition (III)-1 having a mass percentage of 1% by weight was obtained. Note that all the blending amounts of components other than the solvent shown here are the blending amounts of the target product not containing the solvent.

<Production of protective film forming film>
A long second release film ("SP-PET502150" manufactured by Lintec Corporation, thickness 50 μm), which is composed of one side of a polyethylene terephthalate film subjected to release treatment by silicone treatment, is used, and the above-mentioned A thermosetting protective film-forming film having a thickness of 25 μm was produced by applying the protective film-forming composition (III)-1 obtained in step 1 and drying it at 100° C. for 2 minutes.

<Manufacture of protective film forming sheet>
A long release film for removal ("SP-PET381130" manufactured by Lintec Corporation, thickness 38 μm) was prepared by having one side of a polyethylene terephthalate film subjected to release treatment by silicone treatment.
The release-treated surface of the above-mentioned release film for removal was attached to the exposed surface of the protective film-forming film obtained above on the side not provided with the second release film using a laminating roll. This includes a protective film-forming film, a release film for removal provided on one surface of the protective film-forming film, and a second release film provided on the other surface of the protective film-forming film. A long laminated sheet was obtained.

Next, a blade is applied to this laminated sheet from the side of the release film for removal, so that the blade passes through the protective film forming film from the exposed surface of the release film for removal and reaches the inside of the second release film. Two or more circular cuts were formed in the longitudinal direction of the laminated sheet. At this time, in the second release film, the cut was formed to a depth of 15 μm from the surface on the protective film forming film side. In this way, by performing circular punching at two or more locations along the longitudinal direction of the long laminated sheet, the protective film forming film is divided into two or more first regions each having a diameter of 299.5 mm and the other regions. The release film for removal was similarly divided into a first region and a second region. As a result, a first intermediate having a structure similar to that shown in FIGS. 1(a) to 1(b) was obtained.
Next, in this first intermediate, the second region of the protective film-forming film is removed from the second release film together with the second region of the release film for removal attached thereto, and further, the second region of the protective film-forming film is removed from the second release film. A second intermediate was obtained by removing the first region of the release film for removal attached to the first region (removal of residue).

Next, a long first release film ("SP-PET381130" manufactured by Lintec Corporation, thickness 38 μm) was prepared, which was composed of a polyethylene terephthalate film on one side of which was subjected to release treatment by silicone treatment. Then, the first region of all the protective film-forming films in the second intermediate, that is, the exposed surface of two or more circular protective film-forming films with a diameter of 299.5 mm (on the side opposite to the second release film side), Using a laminating roll, apply the release-treated surface of the first release film to the surface of the protective film-forming film. Contact was made in an area other than the vicinity. At this time, the temperature of the laminating roll was 70° C., the application pressure was 0.3 MPa, and the application speed was 10 m/min.
As described above, a long protective film forming sheet having the configuration shown in FIGS. 2(a) and 2(b) was manufactured by the manufacturing method (α).

<<Evaluation of protective film forming sheet>>
<Measurement of peeling force of the first release film against the protective film forming film>
A first test piece with a width of 100 mm and a length of 130 mm was cut out from the protective film forming sheet obtained above. The entire exposed surface of the first test piece on the second release film side (the surface opposite to the protective film forming film side of the second release film) was covered with a general-purpose double-sided tape (Lintec Co., Ltd.), which is an adhesive film for reinforcement. The first test piece was fixed onto the acrylic plate (thickness: 2 mm) by attaching it to the surface of the acrylic plate (thickness: 2 mm) via Tackliner TL-202* (manufactured by Manufacturer, Inc.).
Next, using a tensile tester ("AG-1S" manufactured by Shimadzu Corporation), a first release film was separated from the protective film forming film in this first test piece in an environment of a temperature of 23°C and a relative humidity of 50%. was peeled off. At this time, the first release film was peeled off from the protective film-forming film at a peeling speed of 1000 mm/min such that the surfaces of the first release film and the protective film-forming film that were in contact with each other formed an angle of 180°. (180° peeling was performed). Then, calculate the average value of the peeling force measured after the length of the peeled part of the first release film exceeds 30 mm until the peeling is completed, and use this average value as the peeling force of the first release film. Adopted. The results are shown in the column of "Peeling force of first peeling film (mN/100mm)" in Table 1.

<Measurement of peeling force of the second release film against the protective film forming film>
A section with a width of 120 mm and a length of 145 mm was cut from the protective film forming sheet obtained above. The first release film in this section is peeled off from the protective film-forming film, and polyethylene terephthalate is applied to the entire exposed surface of the newly formed protective film-forming film (the surface opposite to the second release film side). The easily adhesive surfaces of the easily adhesive film (thickness 25 μm, "PET25A-4100" manufactured by Toyobo Co., Ltd.), which is the main component, were bonded together. At this time, using a laminator ("VA-400" manufactured by Taisei Laminator Co., Ltd.), the sheets were bonded together by thermal lamination under conditions of a bonding pressure of 0.3 MPa, a bonding speed of 1 m/min, and a bonding temperature of 70.degree. Then, a second test piece with a width of 100 mm and a length of 130 mm was cut out from the obtained product. The entire exposed surface of this second test piece on the second release film side (the surface opposite to the protective film forming film side of the second release film) was covered with a general-purpose double-sided tape (Lintec Co., Ltd.), which is an adhesive film for reinforcement. The second test piece was fixed onto the acrylic plate (thickness: 2 mm) by attaching it to the surface of the acrylic plate (thickness: 2 mm) via Tackliner TL-202* (manufactured by Manufacturer, Inc.).
Next, using a tensile tester (“AG-1S” manufactured by Shimadzu Corporation), a protective film-forming film was tested from the second release film in this second test piece in an environment of a temperature of 23°C and a relative humidity of 50%. Then, the laminate of the easily adhesive film was peeled off. At this time, the peeling speed was set to 1000 mm/min, and the surfaces of the laminate (more specifically, the protective film forming film in the laminate) and the second release film that were in contact with each other formed an angle of 180°. The laminate was peeled off from the second release film (180° peeling was performed). Then, the average value of the peeling force measured from when the length of the peeled part of the laminate exceeds 30 mm until the peeling is completed is calculated, and this average value is adopted as the peeling force of the second peeling film. did. The results are shown in the column of "Peeling force of second release film (mN/100mm)" in Table 1.

<Calculation of the difference in peeling force between the second release film and the first release film>
The difference between the peeling force of the second peeling film determined above and the peeling force of the first peeling film was calculated. The results are shown in Table 1.

<Evaluation of peelability of first release film>
Using a tape laminator ("RAD-3600F/12" manufactured by Lintec Corporation), the temperature of the rubber roll was set to 60 °C, the temperature of the table was set to 80 °C, and the protective film forming sheet obtained above was used at a peeling speed of 50 mm. While peeling off the first release film at a speed of 50 mm/s and a pressure of 0.25 MPa, 20 protective film-forming films were successively applied one by one to 20 12-inch silicon wafers ( An attempt was made to attach it to a #2000 polished surface with a diameter of 300 mm and a thickness of 300 μm. Then, when the first release film was peeled off, the number of protective film-forming films that were peeled off from the second release film together with the first release film (number of peeled sheets) was confirmed, and the peelability of the first release film was evaluated according to the following criteria. . The results are shown in Table 1.
[Evaluation criteria]
A: The number of peeled protective film forming films is 0, and the peelability of the first peeling film is high.
B: The number of peeled protective film forming films is one, and the peelability of the first peeling film is good.
C: The number of peeled protective film-forming films is two or more, and the peelability of the first peeling film is low.

<Evaluation of the effect of suppressing contamination of silicon wafers by protective film forming film>
When evaluating the releasability of the first release film described above, the outer periphery of all silicon wafers to which the protective film-forming film was attached was measured using a digital microscope (VHS-7000 manufactured by Keyence Corporation) at a magnification of 500 times. observed. Then, the number of silicon wafers on which the protective film forming film was observed to adhere to the outer periphery (number of contaminated sheets) was confirmed, and the effect of suppressing contamination of the silicon wafers by the protective film forming film was evaluated according to the following criteria. The results are shown in Table 1.
[Evaluation criteria]
A: The number of contaminated silicon wafers is 0, and the effect of suppressing contamination by the protective film forming film is high.
B: The number of contaminated silicon wafers is one, and the effect of suppressing contamination by the protective film forming film is good.
C: The number of contaminated silicon wafers is two or more, and the effect of suppressing contamination by the protective film forming film is low.

<<Measurement of adhesion between the first release film and the stainless steel plate>>
After measuring the peeling force of the first release film, the first release film (width 100 mm, length 130 mm) peeled from the protective film forming film is cut to obtain a first release film piece having a width of 25 mm and a length of 130 mm. Two pieces were made. Under the bonding temperature condition of 23° C., the bonding speed was 300 mm/min, and the bonding pressure was 0.3 MPa, the first release film piece was removed from its peel-treated surface (i.e., the surface to which the protective film-forming film had been bonded). A stainless steel plate with a first release film piece was obtained by attaching it to the #600 polished surface of a stainless steel plate (“SUS304 #600 single-sided 600HL 0.5 mm x 70 mm x 150 mm” manufactured by Paltech). Here, "23°C bonding temperature condition" means that the temperature of the laminating roller was 23°C and the temperature of the stainless steel plate was 23°C.
Next, using a tensile testing machine ("AG-1S" manufactured by Shimadzu Corporation), a first peeling test was performed from the stainless steel plate in the stainless steel plate with the first peeling film piece in an environment of a temperature of 23°C and a relative humidity of 50%. The film piece was peeled off. At this time, the peeling speed was set to 300 mm/min, and the first peeling film piece was peeled in the length direction so that the surfaces of the stainless steel plate and the first peeling film piece that were in contact with each other formed an angle of 90°. (90° peeling was performed). Then, the load (adhesive force) during this 90° peeling is measured from the start of measurement to a 110 mm long part of the first release film piece, and from the start of measurement to a 60 mm long part of the first release film piece. The measured value was excluded from the effective values, and the average value of the subsequent measured values was adopted as the adhesive force (mN/25 mm).
The adhesion force was measured twice, and the average value was taken as the adhesion force (mN/25 mm) between the first release film and the stainless steel plate. The results are shown in Table 1.

<<Measurement of adhesion between the second release film and the stainless steel plate>>
After measuring the peeling force of the second release film, the second release film (width 100 mm, length 130 mm) peeled from the protective film forming film is cut to obtain a second release film piece having a width of 25 mm and a length of 130 mm. Two pieces were made. Then, the second release film was measured in the same manner as in the measurement of the adhesive force between the first release film and the stainless steel plate, except that this second release film was used instead of the first release film. The adhesion between the release film and the stainless steel plate was measured. The results are shown in Table 1.

<<Manufacture and evaluation of protective film forming sheet>>
[Example 2]
A protective film-forming sheet was manufactured and evaluated in the same manner as in Example 1, except that the diameter of all circular protective film-forming films was 299 mm instead of 299.5 mm. The results are shown in Table 1.

[Example 3]
A protective film-forming sheet was manufactured and evaluated in the same manner as in Example 1, except that the diameter of all circular protective film-forming films was 285 mm instead of 299.5 mm. The results are shown in Table 1.

[Example 4]
The diameter of all circular protective film-forming films was changed to 299 mm instead of 299.5 mm, and the long first release film was configured by having one side of a polyethylene terephthalate film released by silicone treatment. A protective film forming sheet was formed in the same manner as in Example 1, except that "SP-PET38T124-2, thickness 38 μm) manufactured by Lintec Corporation was used in place of the above-mentioned "SP-PET381130". It was manufactured and evaluated. The results are shown in Table 1.

[Comparative example 1]
A protective film-forming sheet was manufactured and evaluated in the same manner as in Example 1, except that the diameter of all circular protective film-forming films was 300 mm instead of 299.5 mm. The results are shown in Table 1.

[Comparative example 2]
In the same manner as in Example 1, a protective film-forming film, a release film for removal provided on one surface of the protective film-forming film, and a second release film provided on the other surface of the protective film-forming film were prepared. A long laminated sheet comprising a release film and a release film was manufactured. Furthermore, circular notches were formed in this laminated sheet in the same manner as in Example 1, except that the diameter of all circular protective film-forming films was changed to 299 mm instead of 299.5 mm. (Circular punching was performed). Then, without performing the subsequent steps, the laminated sheet after forming the circular cuts (the first intermediate) was used as a long protective film forming sheet for comparison in the same manner as in Example 1. evaluated. That is, in this comparative example, the above-mentioned release film for removal is regarded as a first release film in which a circular cut is formed, and a structure similar to that shown in FIGS. 1(a) and 1(b) is used. The first intermediate having the following was evaluated. The results are shown in Table 1.

As is clear from the above results, in Examples 1 to 4, contamination of the silicon wafer by the protective film forming film was suppressed when the protective film forming film was attached to the silicon wafer (workpiece). In Examples 1 to 4, the diameter of the protective film forming film was 299.5 mm or less, and the difference between the diameter of the silicon wafer and the diameter of the protective film forming film was 0.5 mm or more. In Examples 1 to 4, the diameter of the protective film forming film is 285 mm or more, the difference between the diameter of the silicon wafer and the diameter of the protective film forming film is 15 mm or less, and the protective film forming sheet This did not reduce the production efficiency of the work piece with the protective film.
In Examples 1 to 4, the size of the protective film forming film in the protective film forming sheet is close to the size of the silicon wafer, so no further punching of the protective film forming film is required when using the protective film forming sheet. Therefore, punching of the release film was not necessary.
In Examples 1 to 4, the first release film in the protective film forming sheet did not have any cuts, and the first release film after use was reusable (had reusability). .

In particular, in Examples 2 to 4, the diameter of the protective film-forming film is 299 mm or less, the difference between the diameter of the silicon wafer and the diameter of the protective film-forming film is 1 mm or more, and the protective film-forming film is The effect of suppressing contamination of silicon wafers was high. From this point of view, the protective film forming sheets of Examples 2 to 4 had more preferable characteristics.

In particular, in Examples 1 to 3, the peeling force of the first release film was 70 mN/100 mm, which was a low level, and the peelability of the first release film was high. In Examples 1 to 3, the difference in peel force between the second release film and the first release film was 80 mN/100 mm, which was large. From these viewpoints, the protective film forming sheets of Examples 1 to 3 had more preferable characteristics.

In Examples 1 to 4, the adhesive force between the first release film and the stainless steel plate was 5.3 mN/25 mm or less, and the adhesive force between the second release film and the stainless steel plate was 2.9 mN. /25 mm, and it was presumed that both the first release film and the second release film had a high effect of suppressing winding deviation when wound into a roll.

On the other hand, in Comparative Example 1, the effect of suppressing contamination of the silicon wafer by the protective film forming film was low. In Comparative Example 1, the diameter of the protective film forming film was 300 mm, which was the same as the diameter of the silicon wafer.

In Comparative Example 2, both the first release film and the second release film in the protective film forming sheet had slits, and the used first release film and second release film could not be reused. (was not suitable for reuse).

Up to this point, we have shown examples and comparative examples of protective film-forming sheets that have a circular planar shape as the protective film-forming film. It was recognized that similar evaluation results could be obtained even when a protective film forming sheet having a shape (for example, elliptical) was used.

The present invention can be used to manufacture various substrate devices including semiconductor devices.

1, 2, 3, 4, 5, 6... Sheet for forming a protective film,
11...Protective film forming film, 11a...First surface of the protective film forming film (the surface on the first release film side of the protective film forming film, the side of the protective film forming film on which the first release film was provided) surface), 11b...the second surface of the protective film-forming film (the surface on the second release film side of the protective film-forming film), 11c...the outer periphery of the protective film-forming film,
11'...protective film, 11b'...second surface of the protective film,
12, 22... first release film,
13, 23... second release film, 139... notch in second release film,
101... first laminate, 101'... first laminate in which the protective film forming film is a protective film,
102... second laminate,
109... Semiconductor chip with protective film (workpiece with protective film),
110'...protective film after cutting,
8... Dicing sheet (processing sheet),
81... Base material, 82... Adhesive layer,
9... Semiconductor wafer (work), 9b... Back side of semiconductor wafer (one side of work), 9c... Outer periphery of semiconductor wafer (outer periphery of work),
90... Semiconductor chip (workpiece), 90b... Back side of semiconductor chip (one side of workpiece),
_D9 ...Diameter of semiconductor wafer (diameter of workpiece)
_D11 ...Diameter of protective film forming film

Claims (4)

A sheet for forming a protective film,
The protective film forming sheet includes a first release film, a second release film having a greater release force than the first release film, and a protection film provided between the first release film and the second release film. A film-forming film;
Two or more of the protective film forming films are arranged along the longitudinal direction of one of the first release film and one of the second release film,
The planar shape of the protective film forming film is circular or approximately circular,
The diameter of the protective film forming film is 135 mm or more and less than 150 mm, 185 mm or more and less than 200 mm, 285 mm or more and less than 300 mm, or 435 mm or more and less than 450 mm,
A sheet for forming a protective film, wherein either one or both of the first release film and the second release film does not substantially have a cut at a position that coincides with the outer periphery of the protective film-forming film. The difference between the peeling force of the second release film with respect to the protective film forming film and the peeling force of the first release film with respect to the protective film forming film is 30 mN/100 mm or more and less than 200 mN/100 mm,
The peeling force of the first release film with respect to the protective film forming film is 20 mN/100 mm or more,
The protective film forming sheet according to claim 1, wherein the second release film has a peeling force of 500 mN/100 mm or less with respect to the protective film forming film. The protective film forming sheet according to claim 1 or 2, wherein the first release film does not substantially have the cut. A method for manufacturing a workpiece with a protective film, the method comprising:
The workpiece with a protective film includes a workpiece and a protective film provided on one surface of the workpiece,
The workpiece is obtained by processing a workpiece,
The workpiece has a circular planar shape,
The diameter of the workpiece is 6 inches, 8 inches, 12 inches, or 18 inches,
The protective film is formed from the protective film forming film in the protective film forming sheet according to claim 1 or 2,
When the diameter of the work is 6 inches, the diameter of the protective film forming film is 135 mm or more and less than 150 mm, and when the diameter of the work is 8 inches, the diameter of the protective film forming film is 185 mm. or more and less than 200 mm, and when the diameter of the work is 12 inches, the diameter of the protective film forming film is 285 mm or more and less than 300 mm, and when the diameter of the work is 18 inches, the protective film is The diameter of the formed film is 435 mm or more and less than 450 mm,
When the protective film-forming film is curable, the cured product of the protective film-forming film is the protective film, and when the protective film-forming film is non-curable, any of the works The protective film forming film after being affixed to the location is the protective film,
The manufacturing method includes a first peeling step of peeling the first release film from the protective film forming film in the protective film forming sheet;
After the first peeling step, the surface of the protective film forming film on the side where the first peeling film was provided is removed from the surface of the protective film forming film on the side where the first peeling film was provided, without causing the outer peripheral part of the protective film forming film to protrude from the outer peripheral part of the workpiece. A first pasting step of creating a first laminate in which the protective film forming film or the protective film is provided on the work by pasting it on one side of the work;
After the first pasting step, a second peeling step of peeling the second release film from the protective film forming film or the protective film in the first laminate;
After the second peeling step, a processing sheet for processing the workpiece is attached to the protective film forming film or the surface of the protective film on the side where the second release film was provided. a second pasting step of producing a second laminate in which a sheet, the protective film forming film or the protective film, and the workpiece are laminated in this order in their thickness direction;
a processing step of producing the workpiece by processing the workpiece after the second pasting step;
After the second pasting step, a cutting step of cutting the protective film forming film or the protective film,
When the protective film-forming film is curable, the protective film further comprises, after the second peeling step, a curing step of curing the protective film-forming film to form the protective film. A method for manufacturing a workpiece with a

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