JP2021082767A - Kit, and method for manufacturing third laminate by use thereof - Google Patents

Abstract

To provide: a kit having a protection coat-forming film and a support sheet, by which a third laminate arranged by laminating a workpiece such as a semiconductor wafer, a protection coat-forming film capable of forming a protection film of the workpiece, and a support sheet to be used to support the workpiece and the protection coat-forming film in this order can be suitably manufactured by an in-line process; and a method for manufacturing such a third laminate.SOLUTION: A kit 1 comprises: a first laminate 5 arranged by laminating a first peeling film 151, a protection coat-forming film 13 and a second peeling film 152 in this order; and a support sheet 10. The rupture elongation of the protection coat-forming film at 23°C is larger than 700%.SELECTED DRAWING: Figure 1

Description

The present invention relates to a kit and a method for producing a third laminate using the kit. Specifically, the first laminate in which the first release film, the protective film-forming film, and the second release film are laminated in this order, a work such as a semiconductor wafer to be protected by the protective film-forming film, and the protective film-forming film. A kit including a support sheet used to support the film, and a third laminated body in which the work, the protective film forming film, and the support sheet, which are used in an in-line process, are laminated in this order. Regarding the method.
Here, the "in-line process" is "a process performed in a device in which a plurality (multiple units) of devices performing one or a plurality of processes are connected, or in the same device, and a plurality of processes and the processes and processes thereof. The process of transporting workpieces one by one between one process and the next process, including the transfer of connecting the workpieces.

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

A resin film containing an organic material is formed as a protective film on the back surface of the exposed semiconductor chip, and may be incorporated into a semiconductor device as a semiconductor chip with a protective film. The protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing step or packaging (for example, Patent Documents 1 to 4).

Such a semiconductor chip with a protective film is manufactured, for example, through the process shown in FIG. That is, the protective film forming film 13 is laminated on the back surface 8b of the semiconductor wafer 8 having the circuit surface (FIG. 6 (A)), and the protective film forming film 13 is heat-cured or energy ray-cured to form the protective film 13'(). FIG. 6 (B)), the support sheet 10 is laminated on the protective film 13'(FIG. 6 (D)), and the semiconductor wafer 8 and the protective film 13' are diced to obtain a semiconductor chip 7 with a protective film (FIG. 6 (B)). E) and FIG. 6 (F)), a method of picking up the semiconductor chip 7 with a protective film from the support sheet 10 is known. Here, in FIG. 6A, the apparatus for attaching the protective film forming film 13 to the back surface 8b of the semiconductor wafer 8 and the apparatus in FIG. 6D for attaching the support sheet 10 to the protective film 13'. , It is done in separate devices.

Further, a composite sheet for forming a protective film in which the protective film forming film 13 and the support sheet 10 are integrated is used for manufacturing a semiconductor chip with a protective film (for example, Patent Documents 2, 3 and 4).

A method for manufacturing a semiconductor chip with a protective film using a composite sheet for forming a protective film goes through, for example, the process shown in FIG. 7. That is, the protective film-forming film 13 of the protective film-forming composite sheet 3 in which the protective film-forming film 13 and the support sheet 10 are laminated is attached to the back surface 8b of the semiconductor wafer 8 having the circuit surface (FIG. 7 (A'). )), The back grind tape 17 is peeled off (FIG. 7 (B')), the protective film forming film 13 is heat-cured or energy ray-cured to obtain the protective film 13'(FIG. 7 (C')), and the semiconductor wafer 8 is formed. And the method of dicing the protective film 13'to obtain the semiconductor chip 7 with the protective film (FIGS. 7 (E') and 7 (F')) and picking up the semiconductor chip 7 with the protective film from the support sheet 10 is known. Has been done.

Japanese Patent No. 4271597 International Publication No. 2014/157426 Japanese Patent No. 5363662 Japanese Unexamined Patent Publication No. 2016-225496

In the conventional method for manufacturing a semiconductor chip with a protective film shown in FIG. 6, the work (that is, the semiconductor wafer 8) to be protected by the protective film forming film 13 uses a work whose back grind tape has already been peeled off. There is. A protective film-forming film 13 is laminated on the back surface 8b of the semiconductor wafer 8 (FIG. 6 (A)), and the protective film-forming film 13 is cured to form a protective film 13'(FIG. 6 (B)). Since the support sheet 10 is attached to 13'(FIG. 6 (D)), a device for attaching the protective film forming film 13 to the back surface 8b of the semiconductor wafer 8 and a device for attaching the support sheet 10 to the protective film 13'. It is difficult to make these processes in-line processes because separate devices are used.

In the conventional method for manufacturing a semiconductor chip with a protective film shown in FIG. 7, since the protective film forming composite sheet 3 in which the protective film forming film 13 and the support sheet 10 are integrated is used, the protective film forming film 13 is used. The step of attaching the protective film forming film 13 to the work to be protected (that is, the semiconductor wafer 8) and the step of attaching the support sheet 10 can be combined into one step. However, when the protective film-forming composite sheet 3 is used, the characteristics of the protective film-forming film 13 and the characteristics of the support sheet 10 must be combined in combination, and this is a method for manufacturing a semiconductor chip with a protective film that meets the purpose. In addition, many kinds of composite sheets 3 for forming a protective film must be prepared. Further, in order to prepare the composite sheet 3 for forming the protective film, there is a problem of burden of manufacturing cost such as punching. Further, when the protective film forming composite sheet 3 is used, there is a risk that the tape meanders in the mounter device after the tape roll is installed in the mounting process, and the sticking position and the sticking tension of the first few sheets do not match the settings. There is.

As illustrated in FIG. 8A, the protective film-forming film 13 attached to the work 14 may protrude from the work 14.
In such a case, as illustrated in FIG. 8B, when the second release film 152 of the protective film forming film 13 attached to the work 14 is peeled off, the protective film forming film 13 protruding from the work 14 The protruding portion 90 may be torn off, adhere to the second release film 152, and be taken back.
Further, in such a case, as illustrated in FIG. 8C, when the support sheet 10 is attached to the protective film forming film 13, the protruding portion 90 of the protective film forming film 13 protruding from the work 14 is cracked. There is a risk of scattering.

The present invention has been made in view of the above circumstances, and includes a work such as a semiconductor wafer, a protective film forming film capable of forming a protective film for protecting the back surface of the work and improving the appearance, and the protection. A kit including the protective film-forming film and the support sheet, wherein a third laminate in which the support sheet used for supporting the film-forming film is laminated in this order can be preferably produced by an in-line process. Another object of the present invention is to provide a method for producing a third laminate in which the kit is used in an in-line process.

The present invention provides the following kit and a method for producing a third laminate using the kit.

[1] To support the first laminated body in which the first release film, the protective film forming film and the second release film are laminated in this order, the work to be protected by the protective film forming film, and the protective film forming film. A kit including a support sheet used for
A kit in which the breaking elongation of the protective film-forming film at 23 ° C. is greater than 700%.
[2] The kit according to the above [1], wherein the first laminated body is in the form of a roll.
[3] The kit according to the above [1] or [2], wherein the protective film forming film is thermosetting or energy ray curable.
[4] The kit according to any one of the above [1] to [3], wherein the support sheet is a pressure-sensitive adhesive layer to be attached to the protective film-forming film, which is laminated on a base material.
[5] The peeling force between the protective film-forming film and the second release film is larger than the peeling force between the protective film-forming film and the first release film.
The 180 ° peeling force between the protective film forming film and the second release film measured at a peeling speed of 1 m / min and a temperature of 23 ° C. is 250 mN / 100 mm or less. 4] The kit according to any one of the items.

[6] A third laminated body in which the work, the protective film forming film, and the support sheet, in which the kit according to any one of [1] to [5] is used in an in-line process, are laminated in this order. It ’s a manufacturing method,
The step of peeling the first release film of the first laminated body and
The first laminating step of attaching the exposed surface of the protective film forming film to the work, and
A second laminating step of attaching the support sheet to the surface of the protective film forming film opposite to the exposed surface is included in this order.
A method for manufacturing a third laminated body, wherein the transport distance of the work from the sticking start point of the first laminating step to the sticking completion point of the second laminating step is 7,000 mm or less.

[7] A third laminated body in which the work, the protective film forming film, and the support sheet, in which the kit according to any one of [1] to [5] is used in an in-line process, are laminated in this order. It ’s a manufacturing method,
The step of peeling the first release film of the first laminated body and
The first laminating step of attaching the exposed surface of the protective film forming film to the work, and
A second laminating step of attaching the support sheet to the surface of the protective film forming film opposite to the exposed surface is included in this order.
A method for producing a third laminated body, wherein the transport time of the work from the start of sticking of the first laminating step to the completion of sticking of the second laminating step is 400 s or less.

[8] A third laminated body in which the work, the protective film forming film, and the support sheet, in which the kit according to any one of [1] to [5] is used in an in-line process, are laminated in this order. It ’s a manufacturing method,
The step of peeling the first release film of the first laminated body and
The first laminating step of attaching the exposed surface of the protective film forming film to the work, and
A second laminating step of attaching the support sheet to the surface of the protective film forming film opposite to the exposed surface is included in this order.
A method for producing a third laminated body, in which the second laminated body to which the protective film forming film is attached to the work is conveyed one by one between the first laminating step and the second laminating step.

[9] The method for producing a third laminated body according to any one of the above [6] to [8], wherein the first laminating step is performed on a wafer table at 80 ° C. or higher.
[10] A back grind tape is attached to the surface of the work opposite to the side on which the exposed surface of the protective film-forming film is attached, and after the second laminating step, the work is subjected to the above. The method for producing a third laminate according to any one of [6] to [9] above, which comprises a step of peeling off the back grind tape.
[11] The method for producing a third laminated body according to the above [10], wherein the back grind tape is started to be peeled from the work in less than 10 minutes from the start of application in the first laminating step.

According to the present invention, it is used to support a work such as a semiconductor wafer, a protective film forming film capable of forming a protective film for protecting the back surface of the work and improving the appearance, and the protective film forming film. A third laminated body in which the supporting sheets are laminated in this order can be preferably produced by an in-line process, and a kit including the protective film forming film and the supporting sheet, and the kit are used in the in-line process. A method for producing a third laminated film is provided.

It is the schematic sectional drawing which shows an example of the kit of this embodiment schematically. It is sectional drawing which shows typically an example of the step of peeling off the 1st release film of the 1st laminated body in the manufacturing method of the 3rd laminated body of this embodiment. It is sectional drawing which shows typically an example of the 1st stacking process among the manufacturing method of the 3rd laminated body of this Embodiment. It is sectional drawing which shows typically an example of the 2nd stacking process in the manufacturing method of the 3rd laminated body of this embodiment. It is sectional drawing which shows typically an example in which the back grind tape was able to be peeled off normally from a 3rd laminated body. It is schematic cross-sectional view which shows typically an example of the manufacturing method of the conventional semiconductor chip with a protective film. It is schematic cross-sectional view which shows another example of the conventional manufacturing method of the semiconductor chip with a protective film schematically. It is schematic cross-sectional view which shows typically the example which the protruding part 90 of the protective film forming film was brought back to the heavy surface release film, and the example which was cracked when the support sheet was attached.

Hereinafter, a kit which is an example of an embodiment to which the present invention is applied and a method for producing a third laminate using the kit will be described in detail. In addition, in the drawings used in the following description, in order to make the features easy to understand, the featured parts may be enlarged for convenience, and the dimensional ratio of each component may not be the same as the actual one. Absent.

<< Kit >>
FIG. 1 is a schematic cross-sectional view schematically showing an example of the kit of the present embodiment. The kit of the present embodiment includes a first laminated body 5 in which a first release film 151, a protective film forming film 13 and a second release film 152 are laminated in this order, and a work and protection to be protected by the protective film forming film 13. A support sheet 10 used for supporting the film-forming film 13 is provided.

It is preferable that one of the first release film 151 and the second release film 152 is a light surface release film and the other is a heavy surface release film. In the present embodiment, the first release film 151 is a light surface release film, and the second release film 152 is a heavy surface release film.

Examples of the support sheet 10 include a sheet composed of only the base material 11 and a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer 12 on the base material 11. In the present embodiment, the support sheet 10 has the pressure-sensitive adhesive layer 12 laminated on the base material 11, and after the second release film 152 of the protective film forming film 13 is peeled off, the second release film 152 side is the first. The pressure-sensitive adhesive layer 12 of the support sheet 10 is attached to the two surfaces 13b for use.

<< Manufacturing method of the third laminate using the kit >>
The method for producing the third laminate of the present embodiment is a method for producing the third laminate in which the work, the protective film forming film 13 and the support sheet 10 are laminated in this order, using the kit in an in-line process. , The step of peeling the first release film 151 of the first laminate 5, and the first lamination of attaching the exposed surface of the protective film forming film 13 (that is, the first surface 13a of the protective film forming film 13) to the work. The step and a second laminating step of attaching the support sheet 10 to the surface of the protective film-forming film opposite to the exposed surface (that is, the second surface 13b of the protective film-forming film) are included in this order.

FIG. 2 is an example of a method of using the first laminated body 5, and is a schematic example of a step of peeling the first release film of the first laminated body in the method of manufacturing the third laminated body of the present embodiment. It is sectional drawing which shows.

For the first laminated body 5 (FIG. 2 (a)), for example, a circular punching blade 70 is applied from the side of the first release film 151 to be a light surface release film (FIG. 2 (b)), and the first release film 151 is applied. (Fig. 2 (c)).

FIG. 3 is a cross-sectional schematic view schematically showing an example of the first laminating step in the method for manufacturing the third laminated body of the present embodiment.

In the first laminating step, the first release film 151 of the first laminated body 5 is peeled off from the work 14 (FIG. 3 (a)) to be protected, and the exposed surface of the protective film forming film 13 (circular) ( That is, the first surface 13a) of the protective film forming film 13 is attached (FIGS. 3 (b) and 3 (c)).
Next, the second release film 152 is peeled off to expose the surface of the protective film-forming film 13 opposite to the exposed surface (that is, the second surface 13b of the protective film-forming film) (FIG. 3 (d)).

The first laminating step may be performed on a wafer table at 80 ° C. or higher.
Since the first laminating step is performed on a wafer table at 80 ° C. or higher, the first surface 13a of the protective film forming film 13 has a surface condition or material that makes it difficult for the work 14 to obtain adhesion. Even so, it can be sufficiently adhered to the work 14, whereby the types of work to which the protective film forming film can be applied can be increased.
When the protective film-forming composite sheet 3 is attached to the work 14 on a wafer table at 80 ° C. or higher, the support sheet 10 of the protective film-forming composite sheet 3 is also heated, so that the base material 11 of the support sheet 10 is used. Wrinkles are likely to occur.

As illustrated in FIG. 8A, the protective film-forming film 13 attached to the work 14 may protrude from the wafer. As illustrated in FIG. 8B, when the second release film 152 of the protective film forming film 13 attached to the work 14 is peeled off, the protruding portion 90 of the protective film forming film 13 protruding from the work 14 is It may be torn off, adhere to the second release film 152, and be taken home.

The 180 ° peeling force measured at a peeling speed of 1 m / min and a temperature of 23 ° C. between the protective film forming film 13 and the second peeling film 152 is preferably 250 mN / 100 mm or less. Here, the peeling force between the protective film forming film 13 and the second release film 152 is larger than the peeling force between the protective film forming film 13 and the first release film 151.
The peeling force between the protective film forming film 13 and the second release film 152 can be 250 mN / 100 mm or less, 220 mN / 100 mm or less, 200 mN / 100 mm or less, 180 mN. It can be / 100 mm or less, 160 mN / 100 mm or less, or 140 mN / 100 mm or less. When the peeling force between the protective film forming film 13 and the second peeling film 152 is equal to or less than the above upper limit value, the second peeling film 152 of the protective film forming film 13 attached to the work 14 is peeled off. It is possible to reduce the possibility that the protruding portion 90 of the protective film forming film 13 protruding from the work 14 is torn off and adheres to the second release film 152 and is taken back.

The peeling force between the protective film forming film 13 and the second release film 152 can be 30 mN / 100 mm or more, or 50 mN / 100 mm or more. When the peeling force between the protective film forming film 13 and the second peeling film 152 is at least the above lower limit value, the handleability of the first laminated body 5 can be improved.

The 180 ° peeling force between the protective film forming film 13 and the second release film is measured as follows.
Measuring method: Using a universal tensile tester (manufactured by Shimadzu Corporation, product name "Autograph AG-IS"), in accordance with JIS Z0237: 2009, for a measurement distance of 100 mm, a peeling speed of 1 m / min, temperature 23. Measure at ° C.
Then, the average of the measured values between the measurement distances of 80 mm excluding the beginning 10 mm and the end 10 mm is defined as "180 ° peeling force between the protective film forming film and the second release film".

The protective film-forming film 13 of the present embodiment has a breaking elongation at 23 ° C. of more than 700%. Since the breaking elongation of the protective film-forming film 13 at 23 ° C. is greater than 700%, the protective film-forming film 13 protruding from the work 14 when the support sheet 10 is attached to the protective film-forming film 13. It is possible to reduce the possibility that the protruding portion 90 is cracked and scattered. Further, when the second release film 152 is peeled off, the possibility that the protruding portion 90 of the protective film forming film 13 protruding from the work 14 is torn off can be reduced, so that the second release film 152 adheres to the second release film 152. It is possible to reduce the risk of being taken home.

The elongation at break of the protective film forming film 13 at 23 ° C. can be measured by the following method.
A protective film-forming film having a width of 15 mm, a length of 40 mm, and a thickness of 200 μm was used as a test piece, and the test piece was heated to 23 ° C., and the tensile speed was 100 mm / min and the chuck distance was 10 mm. Measure the amount of elongation when pulled. The elongation at break is obtained from the amount of elongation when the test piece breaks.
Here, the elongation at break is the original length (L) of the amount of increase (ΔL) in the length of the test piece at the time of breaking the test piece in the tensile test based on JISK71161: 2014 (ISO527-1: 2012). It is a ratio.

In the present embodiment, the work 14 is a semiconductor wafer whose one surface is a circuit surface 14a, and the back grind tape 17 may be attached to the circuit surface 14a of the work 14.

FIG. 4 is an example of a method of using the support sheet 10, and is a cross-sectional schematic view schematically showing an example of a second laminating step in the method of manufacturing the third laminated body of the present embodiment.

In the second laminating step, of the second laminated body 6 (FIG. 4D) to which the protective film forming film 13 is attached to the work 14, the surface of the protective film forming film opposite to the exposed surface (that is, protection). The support sheet 10 is attached to the second surface 13b) of the film-forming film (FIGS. 4 (e) and 4 (f)).

In the second laminating step shown in FIG. 4, the support sheet 10 is attached to the second surface 13b of the protective film forming film 13 laminated on the back surface 14b of the work 14. The support sheet 10 is, for example, a circular polypropylene film having a thickness of 80 μm, and is provided with an adhesive layer 16 for a jig on the outer peripheral portion. In the present embodiment, the work 14 is fixed to the fixing jig 18 (for example, a ring frame) together with the protective film forming film 13. Then, the support sheet 10 is attached to the second surface 13b of the protective film forming film 13 and is fixed to the fixing jig 18 (for example, a ring frame) via the jig adhesive layer 16 (FIG. FIG. 4 (e)).
When the support sheet 10 itself has sufficient adhesiveness to the fixing jig 18, the jig adhesive layer 16 does not necessarily have to be provided.

The protective film-forming film 13 of the present embodiment has a breaking elongation at 23 ° C. of more than 700%.
As illustrated in FIG. 8A, the protective film-forming film 13 attached to the work 14 may protrude from the work 14. As illustrated in FIG. 8C, when the support sheet 10 is attached to the protective film forming film 13, the protruding portion 90 of the protective film forming film 13 protruding from the work 14 may crack and scatter.
The elongation at break of the protective film forming film 13 at 23 ° C. can be greater than 700%, greater than 800%, greater than 1000%, or greater than 1200%. It can be greater than 1400%, greater than 1900%, greater than 3000%, greater than 5000%, and greater than 7000%.
Since the breaking elongation of the protective film forming film 13 at 23 ° C. is within the above range, when the support sheet 10 is attached to the protective film forming film 13, the protruding portion 90 of the protective film forming film 13 is cracked and scattered. It is possible to reduce the risk of this.

Conventionally, in FIG. 6A, the apparatus for attaching the protective film forming film 13 to the back surface 8b of the semiconductor wafer 8 and the apparatus in FIG. 6D for attaching the support sheet 10 to the protective film 13' It was carried out in separate devices, and in each laminated body, a plurality of laminated bodies were housed in one cassette and transported to the next device.
However, in the present embodiment, at least between the first laminating step shown in FIG. 3 and the second laminating step shown in FIG. 4, the apparatus for performing the first laminating step and the second laminating step are performed. The protective film forming film 13 is attached to the work 14 between the first laminating step and the second laminating step, which can be performed in the device in which the devices for performing the steps are connected or in the same device. The second laminated body 6 can be conveyed one by one. That is, the second laminated body 6 of the protective film forming film 13 and the work 14 is not housed in the cassette, but is a device that performs the first laminating step in the second laminating step shown in FIG. It can be conveyed in a device in which devices for performing a laminating process are connected or in the same device. As a result, unintentional adhesion of dust and the like can be suppressed and production tact is improved as compared with the case where each process is performed by separate devices.

In the present embodiment, after the first laminating step, the step of peeling the second release film 152 on the side of the second surface 13b from the protective film forming film 13 is also a step of peeling the second release film 152 on the side of the second surface 13b with the apparatus performing the first laminating step and the second laminating The process is performed in a connected device or in the same device. Prior to the first laminating step, the step of peeling the first peeling film 151 on the side of the first surface 13a from the protective film forming film 13 of the first laminated body 5 is also a step of peeling the first laminating film 151 from the apparatus for performing the first laminating step. It is preferable to carry out the second laminating step in a connected device or in the same device.

In the present embodiment, the work 14 is transported from the sticking start point of the first laminating step shown in FIG. 3 (b) to the sticking completion point of the second laminating step shown in FIG. 4 (f). The distance can be designed to be 7,000 mm or less, and the device space can be reduced. The transport distance of the work 14 from the sticking start point of the first laminating step shown in FIG. 3 (b) to the sticking completion point of the second laminating step shown in FIG. 4 (f) is 6500 mm or less. It can be 6000 mm or less, 4500 mm or less, or 3000 mm or less.
When the transport distance of the work 14 from the sticking start point of the first laminating step to the sticking completion point of the second laminating step is within the above range, unintended dust floating in the air on the protective film forming film The risk of sticking can be reduced.

In the present embodiment, the work 14 is conveyed from the start of pasting of the first laminating step shown in FIG. 3 (b) to the completion of pasting of the second laminating step shown in FIG. 4 (f). The time can be reduced to 400 s or less, and the process time can be shortened. The transport time of the work 14 from the start of pasting of the first laminating step shown in FIG. 3 (b) to the completion of pasting of the second laminating step shown in FIG. 4 (f) is 350 s or less. It can be 300 s or less, 250 s or less, 200 s or less, 150 s or less.
Since the transport time of the work 14 from the start of sticking in the first laminating step to the completion of sticking in the second laminating step is not more than the above upper limit value, it is not intended to float in the air on the protective film forming film. The risk of dust adhering can be reduced.
The transport time of the work 14 from the start of pasting in the first laminating step to the completion of pasting in the second laminating step can be 50 s or more, 100 s or more, or 150 s or more. It can also be 200s or more.
The process of transporting the work 14 from the start of pasting of the first laminating step to the completion of pasting of the second laminating step because the transport time of the work 14 is longer than the above lower limit value and the transport is not excessively fast. When the work is moved while being held by the machine arm, the work can be held correctly without dropping. In addition, wear of moving parts of the device can be reduced.

The speed at which the exposed surface of the protective film forming film 13 is attached to the work 14 in the first laminating step, and the support sheet 10 is attached to the surface opposite to the exposed surface of the protective film forming film 13 in the second laminating step. The speed can be 100 mm / sec or less, 80 mm / sec or less, 60 mm / sec or less, or 40 mm / sec or less. When the sticking speed in the first laminating step and the sticking speed in the second laminating step are not more than the above upper limit values, the adhesion between the work 14 and the protective film forming film 13 and the protective film The adhesion between the forming film 13 and the support sheet 10 can be improved.
The sticking speed in the first laminating step and the sticking speed in the second laminating step can be 2 mm / sec or more, 5 mm / sec or more, or 10 mm / sec or more. You can also do it. When the sticking speed in the first laminating step and the sticking speed in the second laminating step are equal to or higher than the lower limit, the production efficiency of the third laminated body 19 is improved and the first laminating is performed. The transport time of the work 14 from the start of sticking of the process to the completion of sticking of the second laminating step can be set to 400 s or less.

In the present embodiment, subsequently, in the device in which the device for performing the first laminating step and the device for performing the second laminating step are connected, or in the same device, the protective film forming film 13 of the support sheet 10 is formed. The back grind tape 17 may be peeled off from the third laminated body 19 by adsorbing the second surface 10b on the opposite side to the suction table 80. FIG. 5 is a schematic cross-sectional view schematically showing an example in which the back grind tape 17 could be normally peeled off from the third laminated body 19.

The method for producing the third laminate of the present embodiment using the kit of the present embodiment is to use the kit in an in-line process. In the present embodiment, after the second laminating step, the step of peeling the back grind tape from the work is also in an apparatus in which the apparatus performing the first laminating step and the apparatus performing the second laminating step are connected. , Or in the same device and in an in-line process.
In the method for producing the third laminated body of the present embodiment, the backgrinding tape can be started to be peeled off from the work in less than 10 minutes from the start of application in the first laminating step. As a result, the risk of mutual migration between the material contained in the support sheet 10 and the material contained in the protective film forming film 13 can be reduced.

In this embodiment, a semiconductor wafer is used as the work 14 shown in FIG. 3 (a). One surface of the semiconductor wafer is the circuit surface 14a, on which bumps are formed. Further, in order to prevent the circuit surface 14a and bumps of the semiconductor wafer from being crushed during backside grinding of the semiconductor wafer and the occurrence of dimples and cracks on the back surface of the wafer, the circuit surface 14a and bumps of the semiconductor wafer are provided with a circuit surface protection tape. Protected by. The circuit surface protection tape is a back grind tape 17, and the back surface of the semiconductor wafer, which is the work 14, (that is, the back surface 14b of the work) is a ground surface.

The work 14 is not limited as long as it has a circuit surface 14a on one side and the other surface can be said to be the back surface. As the work 14, a semiconductor wafer having a circuit surface on one side or individual electronic components are sealed with a sealing resin, and one side has a terminal forming surface (in other words, a circuit surface) of a semiconductor device with terminals. An example includes a semiconductor device panel composed of a semiconductor device assembly with terminals.

As the back grind tape 17, for example, the surface protection sheet disclosed in Japanese Patent Application Laid-Open No. 2016-192488 and Japanese Patent Application Laid-Open No. 2009-141265 can be used. The back grind tape 17 has an adhesive layer having an appropriate removability. The pressure-sensitive adhesive layer may be formed of a general-purpose weak adhesive type pressure-sensitive adhesive such as rubber-based, acrylic-based, silicone-based, urethane-based, and vinyl ether-based. Further, the pressure-sensitive adhesive layer may be an energy ray-curable pressure-sensitive adhesive that is cured by irradiation with energy rays and becomes removable. The back grind tape 17 has a double-sided tape shape, and the outer side of the back grind tape 17 may be fixed to a hard support, or the work 14 may be fixed to a hard support.

As used herein, the term "energy ray" means an electromagnetic wave or a charged particle beam having an energy quantum. Examples of energy rays include ultraviolet rays, radiation, electron beams and the like. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
Further, in the present specification, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" is a property of not being cured by irradiating with energy rays. Means.

<First laminate>
The first laminated body 5 can be prepared, for example, as follows. A solvent-containing protective film-forming composition is applied on the peeling surface of the second release film 152 having a thickness of 38 μm with a knife coater, and then dried in an oven at 120 ° C. for 2 minutes to form a protective film-forming film. To form. Next, the release surface of the first release film 151 having a thickness of 38 μm was overlapped with the protective film-forming film and the two were bonded to each other, and the first release film 151, the protective film-forming film (thickness: 25 μm), and the second release film were attached. The first laminated film 5 made of 152 can be obtained. Such a first laminated body 5 is suitable for storage as, for example, a roll.

The peeled surface of the first release film 151 is, for example, a rough surface having a surface roughness Ra of 200 nm, and the peeled surface of the second release film 152 is smoother than the surface roughness of the rough surface, for example, the surface roughness Ra. The first laminated body 5 can be prepared by setting the smooth surface to 30 nm.

Alternatively, even if the surface roughness Ra of the release surface of the first release film 151 and the surface roughness of the release surface of the second release film 152 are the same smooth surface, for example, the first lamination is performed as follows. Body 5 can be prepared.

That is, a protective film-forming composition containing a solvent is applied to the peeled surface of the second peeling film 152 having a surface roughness Ra of 30 nm with a knife coater, and then dried in an oven at 120 ° C. for 2 minutes. To form a protective film-forming film. Next, the release surface of the first release film 151 having a thickness of 38 μm and a surface roughness Ra of 30 nm was overlapped with the protective film-forming film, and both were bonded together under the conditions of, for example, 23 ° C. and 0.4 MPa. A protective film-forming film composed of 1 release film 151, a protective film-forming film 13 (thickness: 25 μm), and a second release film 152 can be obtained. As a result, the first surface 13a of the protective film forming film 13 and the first release film 151 become a light release surface, and the space between the second surface 13b of the protective film forming film 13 and the second release film 152 is said to be light. It becomes a heavy peeling surface with a peeling strength larger than the peeling strength of the peeling surface. Such a first laminated body 5 is also suitable for storage as, for example, a roll.

The surface roughness of the protective film-forming film on the first release film 151 side can be adjusted by adjusting the temperature and pressure conditions at which the release surface of the first release film 151 is attached to the protective film-forming film. If the temperature and pressure conditions for bonding the release surface of the first release film 151 to the protective film-forming film are increased, the surface roughness of the protective film-forming film on the first release film 151 side can be increased by peeling the first release film 151. Be faithful to the surface roughness of the surface.

The surface roughness Ra of the rough surface of the protective film-forming film facing the back surface side of the work may be 32 to 1200 nm, preferably 32 to 1000 nm, and is preferably 32 to 900 nm. More preferably, it is particularly preferably 32 to 800 nm.

The larger the surface roughness Ra of the rough surface of the protective film forming film, the smaller the area in contact with the release film. Therefore, when the surface roughness Ra of the rough surface of the protective film-forming film is at least the lower limit value, the protective film-forming film is likely to be peeled off preferentially when the rough surface side is peeled off. ..
As a result, when the light surface release film is peeled off, the protective film-forming film is not properly peeled off from the light peeling, and a part of the protective film-forming film remains on the light surface release film, so-called Nakiwakare. The risk of poor peeling can be reduced.

The surface roughness Ra of the smooth surface of the protective film-forming film facing the side of the support sheet is preferably 20 to 80 nm, preferably 24 to 50 nm, and 28 to 32 nm. Is preferable.

The ratio of the surface roughness Ra of the rough surface of the protective film-forming film to the surface roughness Ra of the smooth surface of the protective film-forming film (rough surface surface roughness Ra / smooth surface surface roughness Ra) is , 1.1 to 50, 1.2 to 45, 1.3 to 35, 1.4 to 30, 1.5 to 24. It may be.

(Protective film forming composition)
As the composition of the protective film-forming composition for forming the protective film-forming film, a protective film-forming composition containing no curable component can be used in applications where strong protective performance is not required, and a curing step is not required. So it is easy to use. However, depending on the brittle tip, it may not be possible to obtain sufficient adhesiveness and protective performance. The composition of the protective film-forming composition for forming the protective film-forming film preferably contains a polymer component and a curable component.

The polymer component may also correspond to a curable component. In the present specification, when the protective film-forming composition contains a component corresponding to both the polymer component and the curable component, the protective film-forming composition contains the polymer component and the curable component. Then consider it.

(Polymer component)
A polymer component is used to impart sufficient adhesiveness and film-forming property (sheet-forming property) to the protective film-forming film. As the polymer component, an acrylic polymer, a polyester resin, a urethane resin, an acrylic urethane resin, a silicone resin, a rubber-based polymer, or the like can be used.

The weight average molecular weight (Mw) of the polymer component is preferably 10,000 to 2 million, more preferably 100,000 to 1.2 million, further preferably 200,000 to 1,000,000, and 300,000 to 300,000. It is particularly preferably 900,000. When the weight average molecular weight of the polymer component is at least the above lower limit value, the release film is easily peeled off, and the risk of peeling failure called Nakiwakare is reduced. When the weight average molecular weight of the polymer component is not more than the above upper limit value, it is prevented that the protective film-forming film cannot be attached to the work due to a decrease in adhesiveness, and the protective film-forming film is prevented from peeling off from the work after application. Will be done. Further, when the weight average molecular weight (Mw) is within the above range, it becomes easy to achieve a suitable elongation at break.

The molecular weight distribution (Mw / Mn) is preferably 4 or more, more preferably 4.2 or more, further preferably 4.5 or more, and particularly preferably 5.5 or more. Most preferably, it is 7 or more. By setting the molecular weight distribution to the above lower limit value or more, molecules having various molecular weights are present in the polymer component, so that the protective film-forming film 13 can easily achieve a large elongation at break.
The molecular weight distribution (Mw / Mn) is preferably 14 or less, more preferably 12 or less, further preferably 11 or less, and particularly preferably 10 or less. By setting the molecular weight distribution to the above upper limit value or less, the adhesion reliability between the work 14 and the protective film forming film 13 can be improved.
Here, Mn is a number average molecular weight.

The weight average molecular weight (Mw) and number average molecular weight (Mn) values of each component are standard polystyrene-equivalent values measured by gel permeation chromatography (GPC).

Acrylic polymer is preferably used as the polymer component. The glass transition temperature (Tg) of the acrylic polymer is preferably -60 to 50 ° C, more preferably -50 to 40 ° C, further preferably -40 to 30 ° C, for example -30. It may be ~ 20 ° C., 25-15 ° C., or −20-10 ° C.
When the glass transition temperature of the acrylic polymer is at least the above lower limit value, the release film is easily peeled off, and the risk of peeling failure called Nakiwakare is reduced. When the glass transition temperature of the acrylic polymer is equal to or lower than the above upper limit, it is prevented that the protective film-forming film cannot be attached to the work due to a decrease in adhesiveness, and the protective film-forming film is prevented from peeling from the work after application. In addition, the risk of cracks occurring when the protective film-forming film is bent as a roll is reduced. Further, when the glass transition temperature (Tg) is in the above range, it becomes easy to achieve a suitable elongation at break.

From the viewpoint of adhesiveness and film-forming property, the preferable content of the polymer component is preferably 5 to 80 parts by mass and 8 to 70 parts by mass with respect to 100 parts by mass of the total weight of the protective film-forming film. More preferably, it is 11 to 60 parts by mass, and for example, it may be 14 to 50 parts by mass, 17 to 45 parts by mass, or 20 to 40 parts by mass. When the content of the polymer component is within the above range, it becomes easy to achieve a suitable elongation at break.

The glass transition temperature (Tg) of the resin constituting the polymer component can be obtained by calculation using the Fox formula shown below.
1 / Tg = (W1 / Tg1) + (W2 / Tg2) + ... + (Wm / Tgm)
(In the formula, Tg is the glass transition temperature of the resin constituting the polymer component, and Tg1, Tg2, ... Tgm is the glass transition temperature of the homopolymer of each monomer which is the raw material of the resin constituting the polymer component. Yes, W1, W2, ... Wm is the mass fraction of each monomer. However, W1 + W2 + ... + Wm = 1.)
For the glass transition temperature of the homopolymer of each monomer in the Fox formula, the value described in the adhesive handbook, Polymer Handbook, or the like can be used. For example, the glass transition temperature of a homopolymer is 10 ° C for methyl acrylate, 105 ° C for methyl methacrylate, -15 ° C for 2-hydroxyethyl acrylate, -54 ° C for n-butyl acrylate, and 41 ° C for glycidyl methacrylate. is there.

Examples of the monomer constituting the acrylic polymer include a (meth) acrylic acid ester monomer or a derivative thereof. For example, alkyl (meth) acrylates having an alkyl group having 1 to 18 carbon atoms, specifically methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl. Examples include (meth) acrylate. Further, a (meth) acrylate having a cyclic skeleton, specifically, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Examples thereof include dicyclopentenyloxyethyl (meth) acrylate and imide (meth) acrylate. Further, examples of the monomer having a functional group include hydroxymethyl (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like; and glycidyl (meth) having an epoxy group. Examples include acrylate. As the acrylic polymer, an acrylic polymer containing a monomer having a hydroxyl group is preferable because it has good compatibility with a curable component described later. Further, the acrylic polymer may be copolymerized with acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and the like.

Further, as a polymer component, a thermoplastic resin for maintaining the flexibility of the protective film after curing may be blended. As such a thermoplastic resin, one having a weight average molecular weight of 10 to 100,000 is preferable, and one having a weight average molecular weight of 3000 to 80,000 is more preferable. The glass transition temperature of the thermoplastic resin is preferably -30 to 120 ° C, more preferably -20 to 120 ° C. Examples of the thermoplastic resin include polyester resin, urethane resin, phenoxy resin, polybutene, polybutadiene, polystyrene and the like. These thermoplastic resins can be used alone or in admixture of two or more. By containing the above-mentioned thermoplastic resin, the protective film-forming film follows the transfer surface of the protective film-forming film, and the generation of voids and the like can be suppressed.

(Curable component)
As the curable component, a thermosetting component and / or an energy ray curable component is used. Thereby, the protective film forming film can be made thermosetting and / or energy ray curable.

By using a thermosetting protective film-forming film, thermosetting can be easily performed even if the protective film-forming film is thickened, so that the protective film-forming film having good protective performance can be thickened. In the heat curing step, a large number of workpieces can be cured at once.

By using the energy ray-curable protective film-forming film, the energy ray-curing of the protective film-forming film can be performed in a short time.

As the thermosetting component, a thermosetting resin and a thermosetting agent are used. As the thermosetting resin, for example, an epoxy resin is preferable.

As the epoxy resin, a conventionally known epoxy resin can be used. Specific examples of the epoxy resin include polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, and bisphenol. Examples thereof include epoxy compounds having bifunctionality or higher in the molecule, such as A-type epoxy resin, bisphenol F-type epoxy resin, and phenylene skeleton-type epoxy resin. These can be used alone or in combination of two or more.

The preferable content of the thermosetting component is preferably 1 to 75 parts by mass, more preferably 2 to 65 parts by mass, and 3 to 60 parts by mass with respect to 100 parts by mass of the total weight of the protective film forming film. It is more preferable, for example, it may be 4 to 55 parts by mass, 5 to 50 parts by mass, or 6 to 45 parts by mass.
When the content of the thermosetting resin is at least the above lower limit value, the protective film can obtain sufficient adhesiveness to the work, the performance of the protective film to protect the work is excellent, and when it is at least the above upper limit value, the roll Excellent storage stability when stored as a body.

The thermosetting agent functions as a curing agent for thermosetting resins, particularly epoxy resins. Preferred thermosetting agents 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 carboxyl group and an acid anhydride. Of these, phenolic hydroxyl groups, amino groups, acid anhydrides and the like are preferable, and phenolic hydroxyl groups and amino groups are more preferable.

Specific examples of the phenol-based curing agent include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, zylock-type phenol resins, and aralkyl phenol resins. Specific examples of the amine-based curing agent include DICY (dicyandiamide). These can be used alone or in combination of two or more.

The content of the thermosetting agent is preferably 0.1 to 500 parts by mass, and more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the thermosetting resin. When the content of the thermosetting agent is at least the above lower limit value, it is sufficiently cured and adhesiveness is obtained, and when it is at least the above upper limit value, the hygroscopicity of the protective film is suppressed and the adhesion reliability between the work and the protective film is improved. To do.

As the energy ray-curable component, a low molecular weight compound (energy ray-polymerizable compound) containing an energy ray-polymerizable group and polymerizing and curing when irradiated with energy rays such as ultraviolet rays and electron beams can be used. Specifically, as such an energy ray-curable component, trimethylolpropantriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or 1,4-butylene glycol. Examples thereof include acrylate-based compounds such as diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate-based oligomer, epoxy-modified acrylate, polyether acrylate and itaconic acid oligomer. Such compounds have at least one polymerizable double bond in the molecule and usually have a weight average molecular weight of about 100 to 30,000, preferably about 300 to 10000. The preferable content of the energy ray-curable component is preferably 1 to 80 parts by mass, more preferably 2 to 70 parts by mass, and 3 to 60 parts by mass with respect to 100 parts by mass of the total weight of the protective film forming film. Is more preferable, for example, it may be 4 to 50 parts by mass, or 5 to 40 parts by mass.

The main skeleton of the energy ray-curable polymer is not particularly limited, and may be an acrylic polymer that is widely used as a polymer component, or may be polyester, polyether, or the like, but synthesis and control of physical properties may be used. It is particularly preferable to use an acrylic polymer as a main skeleton because it is easy to use.

The energy ray-polymerizable group bonded to the main chain or side chain of the energy ray-curable polymer is, for example, a group containing an energy ray-polymerizable carbon-carbon double bond, specifically, a (meth) acryloyl group or the like. Can be exemplified. The energy ray-polymerizable group may be bonded to the energy ray-curable polymer via an alkylene group, an alkyleneoxy group, or a polyalkyleneoxy group.

The weight average molecular weight (Mw) of the energy ray-curable polymer to which the energy ray-polymerizable group is bonded is preferably 10,000 to 2 million, more preferably 100,000 to 1.5 million. The glass transition temperature (Tg) of the energy ray-curable polymer is preferably in the range of -60 to 50 ° C, more preferably -50 to 40 ° C, and particularly preferably -40 to 30 ° C.

The energy ray-curable polymer is, for example, an acrylic polymer containing a functional group such as a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, or an epoxy group, and a substituent and an energy ray-polymerizable carbon that react with the functional group. It is obtained by reacting with a polymerizable group-containing compound having 1 to 5 carbon double bonds per molecule. Examples of the substituent that reacts with the functional group include an isocyanate group, a glycidyl group, a carboxyl group and the like.

Examples of the polymerizable group-containing compound include (meth) acryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, allyl isocyanate, glycidyl (meth) acrylate; (meth) acrylic acid and the like. Can be mentioned.

The acrylic polymer is a (meth) acrylic monomer having a functional group such as a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, or an epoxy group or a derivative thereof, and another (meth) acrylic acid ester monomer copolymerizable therewith. Alternatively, it is preferably a copolymer composed of a derivative thereof.

Examples of the (meth) acrylic monomer having a functional group such as a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group or a derivative thereof include 2-hydroxyethyl (meth) acrylate having a hydroxyl group and 2-hydroxy. Propyl (meth) acrylate; acrylic acid having a carboxyl group, methacrylic acid, itaconic acid; glycidyl methacrylate having an epoxy group, glycidyl acrylate and the like can be mentioned.

As another (meth) acrylic acid ester monomer or a derivative thereof that can be copolymerized with the above monomer, for example, an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms, specifically a methyl (meth) acrylate. , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like; (meth) acrylate having a cyclic skeleton, specifically cyclohexyl (meth) acrylate, Examples thereof include benzyl (meth) acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, and imide acrylate. Further, vinyl acetate, acrylonitrile, styrene and the like may be copolymerized with the acrylic polymer.

Even when an energy ray-curable polymer is used, the above-mentioned energy ray-polymerizable compound may be used in combination, or a polymer component may be used in combination. Regarding the relationship between the blending amounts of these three in the protective film-forming film in the present invention, the energy ray-polymerizable compound is preferably 1 to 100 parts by mass, which is the sum of the masses of the energy ray-curable polymer and the polymer components. It is contained in an amount of 1500 parts by mass, more preferably 10 to 500 parts by mass, and particularly preferably 20 to 200 parts by mass.

As described above, the curing conditions for forming the protective film by thermosetting the thermosetting protective film forming film are particularly limited as long as the degree of curing is such that the protective film sufficiently exerts its function. However, it may be appropriately selected depending on the type of the thermosetting protective film-forming film.

The curing conditions when the energy ray-curable protective film forming film is energy-cured to form the protective film are not particularly limited as long as the degree of curing is such that the protective film sufficiently exerts its function. It may be appropriately selected depending on the type of the linear curable protective film forming film.
For example, the illuminance of the energy ray at the time of energy ray curing of the energy ray curable protective film forming film is preferably ^{4 to 280 mW / cm 2.} The amount of light of the energy rays at the time of curing is preferably ^{3 to 1000 mJ / cm 2.}

The protective film-forming film can contain the following components in addition to the above-mentioned polymer component and curable component.

(Colorant)
The protective film-forming film preferably contains a colorant. By blending a colorant in the protective film-forming film, it is possible to block infrared rays and the like generated from surrounding devices when the semiconductor device is incorporated into a device, and prevent the semiconductor device from malfunctioning due to them. The visibility of characters when a product number or the like is printed on the protective film obtained by curing the protective film forming film is improved. That is, in a semiconductor device or semiconductor chip on which a protective film is formed, a product number or the like is usually printed on the surface of the protective film by a laser marking method (a method of scraping the surface of the protective film with laser light to perform printing), but the protective film is printed. By containing the colorant, a sufficient contrast difference between the portion scraped by the laser beam of the protective film and the portion not scraped by the laser beam can be sufficiently obtained, and the visibility is improved. As the colorant, organic or inorganic pigments and dyes are used. Pigments are preferable from the viewpoint of heat resistance and the like. As the pigment, carbon black, iron oxide, manganese dioxide, aniline black, activated carbon and the like are used, but the pigment is not limited thereto. Among them, carbon black is particularly preferable from the viewpoint of handleability and dispersibility. As the colorant, one type may be used alone, or two or more types may be used in combination.

The blending amount of the colorant is preferably 0.01 to 35 parts by mass, more preferably 0.02 to 15 parts by mass, and further preferably 0.% by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming film. It may be 03 to 10 parts by mass, for example, 0.04 to 5 parts by mass, 0.05 to 1.5 parts by mass, or 0.06 to 1 part by mass. .. When the blending amount of the colorant is not more than the above upper limit value, it is easy to confirm the presence or absence of floating when the work piece 14 is attached, and when it is not more than the above lower limit value, the cracking phenomenon and the take-out phenomenon are confirmed. It will be easier.

(Curing accelerator)
The curing accelerator is used to adjust the curing rate of the protective film forming film. The curing accelerator is preferably used when the epoxy resin and the thermosetting agent are used in combination, especially in the curable component.

Preferred curing accelerators are tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine; Examples thereof include tetraphenylborone salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate. These can be used alone or in combination of two or more.

The curing accelerator is contained in an amount of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the curable component. By containing the curing accelerator in an amount in the above range, it has excellent adhesive properties even when exposed to high temperature and high humidity, and achieves high adhesive reliability even when exposed to severe reflow conditions. can do.

(Coupling agent)
The coupling agent may be used to improve the adhesive reliability of the protective film to the work. Further, by using the coupling agent, the water resistance of the protective film formed by curing the protective film can be improved without impairing the heat resistance of the protective film.

As the coupling agent, a compound having a group that reacts with a functional group of a polymer component, a curable component, or the like is preferably used. As the coupling agent, a silane coupling agent is desirable. Examples of such a coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ- (methacryloxypropyl). ) Trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N- Phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxy Examples thereof include silane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane. These can be used alone or in combination of two or more.

The coupling agent is usually 0.03 to 20 parts by mass, preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total of the polymer component and the curable component. Is included in the ratio of. If the content of the coupling agent is less than 0.03 parts by mass, the above effect may not be obtained, and if it exceeds 20 parts by mass, it may cause outgas.

(Filler)
By blending the filler into the protective film forming film, it is possible to adjust the coefficient of thermal expansion of the protective film after curing, and by optimizing the coefficient of thermal expansion of the protective film after curing for the semiconductor chip. The adhesion reliability between the work and the protective film can be improved. As the filler, an inorganic filler is preferable. It is also possible to reduce the hygroscopicity of the protective film after curing.

Preferred inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride and the like, spherical beads thereof, single crystal fibers and glass fibers. Among these, silica filler and alumina filler are preferable. The inorganic filler can be used alone or in combination of two or more. The content of the inorganic filler may be, for example, 80 parts by mass or less, 1 to 70 parts by mass, or 2 to 70 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming film. It can be 65 parts by mass, 3 to 60 parts by mass, 5 to 55 parts by mass, 10 to 50 parts by mass, or 15 to 45 parts by mass. You can also.
By setting the content of the inorganic filler to the above upper limit value or less, the risk of cracking when the protective film forming film is bent into a roll body can be reduced, and the content is equal to or more than the above lower limit value. By doing so, the heat resistance of the protective film can be improved. By setting the content of the inorganic filler within the above range, it becomes easy to achieve a suitable elongation at break, and it becomes easy to achieve a suitable peeling force of the heavy surface release film 152.

(Photopolymerization initiator)
When the protective film-forming film contains an energy ray-curable component as the above-mentioned curable component, the energy ray-curable component is cured by irradiating with energy rays such as ultraviolet rays when using the protective film-forming film. At this time, by incorporating the photopolymerization initiator in the composition, the polymerization curing time and the amount of light irradiation can be reduced.

Specific examples of such photopolymerization initiators include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2, 4-diethylthioxanthone, α-hydroxycyclohexylphenylketone, benzyldiphenylsulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, 1,2-diphenylmethane, 2-hydroxy-2-methyl Examples thereof include -1- [4- (1-methylvinyl) phenyl] propanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and β-chloranthraquinone. The photopolymerization initiator may be used alone or in combination of two or more.

The blending ratio of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the energy ray-curable component. When it is above the above lower limit value, satisfactory protection performance can be obtained by photopolymerization, and when it is below the above upper limit value, the formation of residues that do not contribute to photopolymerization is suppressed and the curability of the protective film forming film is sufficient. Can be

(Crosslinking agent)
A cross-linking agent can also be added to adjust the adhesive strength and cohesiveness of the protective film-forming film to the work. Examples of the cross-linking agent include an organic polyvalent isocyanate compound and an organic polyvalent imine compound.

Examples of the organic polyvalent isocyanate compound include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimerics of these organic polyvalent isocyanate compounds, and these organic polyvalent isocyanate compounds. Examples thereof include a terminal isocyanate urethane prepolymer obtained by reacting with a polyol compound.

Examples of the organic polyvalent isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and diphenylmethane. -2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, trimethylpropane adduct tolylene diisocyanate and lysine Isocyanate can be mentioned.

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

The cross-linking agent is usually 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymer component and the energy ray-curable polymer. Used in proportions of parts.

(General-purpose additive)
In addition to the above, various additives may be added to the protective film-forming film, if necessary. Examples of various additives include tackifiers, leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents and the like.

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

The solvent contained in the protective film-forming composition is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the adhesive composition can be mixed more uniformly.

The protective film-forming film obtained by applying and drying the protective film-forming composition composed of the above components has adhesiveness and curability, and in an uncured state, the work (semiconductor wafer, chip, etc.) ) To adhere. The protective film-forming film may be heated when pressed. After curing, a protective film having high impact resistance can be finally provided, the adhesive strength is excellent, and a sufficient protective function can be maintained even under severe high temperature and high humidity conditions. The protective film-forming film may have a single-layer structure, or may have a multi-layer structure as long as it contains one or more layers containing the above components.

The thickness of the protective film-forming film is not particularly limited, but may be 3 to 300 μm, 3 to 200 μm, 5 to 100 μm, 7 to 80 μm, or 10 It can be ~ 70 μm, 12-60 μm, 15-50 μm, 18-40 μm, 20-30 μm.
When the thickness of the protective film forming film is at least the above lower limit value, the protective performance of the protective film can be made sufficient, and when it is at least the above upper limit value, the cost is reduced and the energy ray curable protective film is made. The energy rays can reach the inside of the forming film.

<Support sheet>
Examples of the support sheet used in one aspect of the present invention include a sheet composed of only a base material and a pressure-sensitive adhesive sheet in which an adhesive layer is laminated on the base material.
The support sheet is attached to a release sheet that prevents dust from adhering to the surface of the protective film forming film, or a fixing jig such as a ring frame and a work with the protective film forming film, and the machine arm directly attaches the protective film. It plays the role of a transport sheet or the like that can hold and transport the fixing jig without touching the work with the forming film.

The thickness of the support sheet is appropriately selected depending on the intended use, but is preferably 10 to 500 μm, more preferably 20 to 500 μm, from the viewpoint of improving the adhesiveness to the work with the protective film forming film and the fixing jig. It is 350 μm, more preferably 30 to 200 μm.
The thickness of the support sheet includes not only the thickness of the base material constituting the support sheet but also the thickness of those layers and the film when the adhesive layer is provided, but the protective film-forming film. Does not include release films that are not attached to.

(Base material)
A resin film is preferable as the base material constituting the support sheet.
Examples of the resin film include polyethylene films such as low-density polyethylene (LDPE) films and linear low-density polyethylene (LLDPE) films, ethylene / propylene copolymer films, polypropylene films, polybutene films, polybutadiene films, and polymethylpentene. Film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene / vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic Examples thereof include acid copolymer films, ethylene / (meth) acrylic acid ester copolymer films, polystyrene films, polycarbonate films, polyimide films, and fluororesin films.
The base material used in one aspect of the present invention may be a single-layer film composed of one type of resin film, or may be a laminated film in which two or more types of resin films are laminated.
Further, in one aspect of the present invention, a sheet obtained by subjecting the surface of a base material such as the above-mentioned resin film to a surface treatment may be used as a support sheet.

These resin films may be crosslinked films.
Further, colored resin films or printed ones can also be used.
Further, the resin film may be a sheet obtained by extruding a thermoplastic resin or may be a stretched resin film, or a curable resin thinned and cured by a predetermined means to form a sheet. May be used.

Among these resin films, a base material containing a polypropylene film is preferable from the viewpoint that it has excellent heat resistance, has expandability because it has appropriate flexibility, and easily maintains pickup suitability.
The base material containing the polypropylene film may have a single-layer structure composed of only the polypropylene film or a multi-layer structure composed of the polypropylene film and another resin film.
When the protective film-forming film is thermosetting, the resin film constituting the base material has heat resistance, so that damage due to heat of the base material can be suppressed, and the occurrence of defects in the manufacturing process of the semiconductor device can be suppressed.

The thickness of the base material constituting the support sheet is preferably 10 to 500 μm, more preferably 15 to 300 μm, and even more preferably 20 to 200 μm.

(Adhesive sheet)
Examples of the pressure-sensitive adhesive sheet used as the support sheet 10 in one aspect of the present invention include those having a pressure-sensitive adhesive layer 12 formed from a pressure-sensitive adhesive on a base material 11 such as the above-mentioned resin film. By having the pressure-sensitive adhesive layer 12, the 180 ° peeling adhesive force between the protective film-forming film and the support sheet can be easily adjusted.

Examples of the pressure-sensitive adhesive that is a material for forming the pressure-sensitive adhesive layer include a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive resin, and the pressure-sensitive adhesive composition further contains a general-purpose additive such as the above-mentioned cross-linking agent and pressure-sensitive adhesive. You may.
Examples of the adhesive resin include acrylic resin, urethane resin, rubber resin, silicone resin, vinyl ether resin, and the like when focusing on the structure of the resin, and when focusing on the function of the resin. For example, an energy ray-curable pressure-sensitive adhesive and the like can be mentioned.

The support sheet 10 may be composed of one layer (single layer) or may be composed of two or more layers. When the support sheet is composed of a plurality of layers, the constituent materials and the thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

In the present specification, not only in the case of the support sheet, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers are different". It means that only some of the layers may be the same, and further, "multiple layers are different from each other" means that "at least one of the constituent materials and thicknesses of each layer is different from each other". Means.

The support sheet may be transparent, opaque, or colored depending on the purpose.
For example, when the protective film-forming film has energy ray curability, the support sheet preferably allows energy rays to pass through.
For example, in order to optically inspect the protective film-forming film via the support sheet, the support sheet is preferably transparent.
From the viewpoint of improving handleability, the support sheet may be provided with a release film before being attached to the protective film-forming film.

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

[Preparation of protective film forming composition]
The following components are mixed at the respective compounding ratios (solid content conversion) shown in Tables 1 and 2, and methyl ethyl ketone so that the solid content concentration is 50% by mass with respect to the total mass of the protective film-forming composition. Diluted with, each protective film-forming composition for forming a protective film-forming film of a semiconductor wafer was prepared.

(A-1): Polymer component: Acrylic polymer obtained by copolymerizing 4 parts by mass of butyl acrylate, 82 parts by mass of methyl acrylate, 4 parts by mass of glycidyl methacrylate, and 10 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight). : 350,000, molecular weight distribution (Mw / Mn): 4.4). The glass transition temperature of this component is 5 ° C.
(A-2) Acrylic polymer obtained by copolymerizing 10 parts by mass of butyl acrylate, 80 parts by mass of methyl acrylate, 4 parts by mass of glycidyl methacrylate, and 6 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 390,000, molecular weight). Distribution (Mw / Mn): 7.8). The glass transition temperature of this component is 1 ° C.

(B-1) Thermosetting resin: Bisphenol A type epoxy resin: Mitsubishi Chemical Corporation, jER828, epoxy equivalent 184 to 194 g / eq
(B-2) Thermosetting resin: Dicyclopentadiene type epoxy resin: DIC Corporation, Epicron HP-7200HH, epoxy equivalent 255-260 g / eq
(B-3) Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1055, epoxy equivalent 800-900 g / eq)

(C-1) Thermosetting agent: Thermosetting latent epoxy resin curing agent (dicyandiamide (manufactured by Mitsubishi Chemical, DICY7 active hydrogen amount 21 g / eq))
(D-1) Curing Accelerator: 2-Phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemicals Corporation, Curesol® 2PHZ)
(E-1) Filler: Silica filler (manufactured by Admatex, SC105G-MMQ (average particle size 300 nm))
(F-1) Colorant: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA600)
(G-1) Coupling agent: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.

[Preparation of the first laminate]
A double-sided release film (corresponding to the second release film) in which one side of a 50 μm-thick polyethylene terephthalate (PET) film is peeled by a silicone treatment (A. Lintec's “SP-PET50131” or B. Each of the protective film forming compositions was applied to the peeled surface of Lintec Corporation "SP-PET502150") with a knife coater to form a coating layer. By drying at 110 ° C. for 2 minutes, protective film-forming films of Examples 1 to 8 and Comparative Examples 1 and 2 having a thickness of 25 μm were formed.
Further, a light surface peeling is performed by separately peeling one side of a polyethylene terephthalate (PET) film on the exposed surface (the surface opposite to the side provided with the release film) of the protective film forming film by a silicone treatment. The peeling surface of the film (“SP-PET381130” manufactured by Lintec Co., Ltd., thickness 38 μm, corresponding to the first release film) is subjected to conditions of temperature: 60 ° C. ± 5 ° C., pressure: 0.4 MPa, speed: 1 m / min. To prepare a laminated sheet (that is, the first laminated body of Examples 1 to 8 and Comparative Examples 1 and 2) in which a release film was laminated on both sides of the protective film-forming film.

(Adhesive composition)
The pressure-sensitive adhesive composition used in the production of the support sheet consisted of 100 parts by mass (solid content) of the polymer component and 5 parts by mass of a trifunctional xylylene diisocyanate-based cross-linking agent (“Takenate (registered trademark) D110N” manufactured by Takeda Pharmaceutical Company Limited). It contains (solid content), and the solid content concentration is adjusted to 30% by mass using a mixed solvent of methyl ethyl ketone, toluene, and ethyl acetate.
The polymer component is 70 parts by mass of 2-ethylhexyl acrylate (hereinafter, may be abbreviated as "2EHA") and 20 parts by mass of methyl methyl methacrylate (hereinafter, may be abbreviated as "MMA"). And 10 parts by mass of 2-hydroxylethyl acrylate (hereinafter, may be abbreviated as "HEA") are copolymerized to obtain an acrylic copolymer having a weight average molecular weight of 500,000.

[Manufacturing of support sheet with release film]
The pressure-sensitive adhesive composition is applied to the peel-processed surface of the release film (Lintec's "SP-PET382150", thickness 38 μm) with a knife coater, dried at 110 ° C. for 2 minutes, and the pressure-sensitive adhesive layer (after drying). A polypropylene film (thickness 80 μm, manufactured by Gunze Co., Ltd., glossy surface), which is a base material, is separately formed on the exposed surface (the surface opposite to the side provided with the release film) to form a thickness (10 μm). A glossy surface having a surface roughness of 0.1 μm and a matte surface of 0.3 μm) was bonded to obtain a support sheet with a release film having a structure of a base material / adhesive layer / release film.

Hereinafter, the kit provided with the first laminated body of Example 1 and the support sheet is referred to as the kit of Example 1, and similarly, the first laminated bodies of Examples 2 to 5 and the support sheet are used. The kits including the above are referred to as the kits of Examples 2 to 5, respectively, and the kits including the first laminate of Comparative Example 1 and the support sheet are referred to as the kits of Comparative Example 1, respectively.

[Composite (integrated) sheet for forming protective film)]
The light surface release film of the first laminated body of Comparative Example 2 (composed of a light surface release film / protective film forming film / heavy surface release film) was peeled off, and the above-mentioned support sheet release film (SP) was applied to the exposed surface of the light surface release film. -PET382150) was peeled off and laminated on the exposed pressure-sensitive adhesive layer surface at 23 ° C., and a laminate sample of Comparative Example 2 was prepared, which consisted of a base material / pressure-sensitive adhesive layer / protective film forming film / double surface release film. .. All of these operations were carried out in an environment of 23 ° C.

<Attachment of wafer>
First, a silicon wafer (200 mm diameter, thickness 350 μm) to which a back grind tape (ADWILL E-8180HR manufactured by Lintec Corporation) was attached and polished by # 2000 was prepared. The light surface release film of the first laminate (composed of a light surface release film / protective film forming film / heavy surface release film) of Examples 1 to 8 and Comparative Example 1 was peeled off, and silicon was applied to these exposed surfaces. The table temperature was adjusted by using a sticking device (the "RAD-3600F / 12" part in the connecting device of "RAD (registered trademark) -3600F / 12" and "RAD-2700F / 12" manufactured by Lintec Corporation) to attach the polished surface of the wafer. The film was applied at 23 ° C., 60 ° C., and 80 ° C., and the speed was set at 20 mm / sec. Next, the support sheet with the release film was punched into a circular shape having a diameter of 203 mm in advance, and the light surface release film was peeled off. Next, the heavy surface release film of the wafer / protective film forming film / heavy surface release film is peeled off, and the exposed surface of the support sheet from which the light surface release film has been peeled off in advance is attached to these exposed surfaces (the connection). Using the "RAD-2700F / 12" portion of the device), the temperature was set to 23 ° C., the speed was set to 20 mm / sec, and the film was applied. At this time, the support sheet was also attached to the ring frame for the 8-inch wafer. Then, the back grind tape was peeled off from the wafer / protective film forming film / support sheet. A series of steps from the step of peeling the light surface release film from the first laminate to the step of peeling the back grind tape were performed by an in-line process.
The transport distance of the silicon wafer from the point where the silicon wafer was started to be attached to the protective film-forming film to the point where the support sheet was completely attached to the protective film-forming film was 5000 mm.
The transport time of the silicon wafer from the time when the silicon wafer was started to be attached to the protective film-forming film to the time when the support sheet was completely attached to the protective film-forming film was 300 s. In the present specification, this transport time may be simply referred to as "transport time".
The time from the start of attaching the silicon wafer to the protective film-forming film to the start of peeling the backgrinding tape from the silicon wafer was 7 min.

When the work of attaching the wafer and the support sheet to the first laminated body of Example 1 was repeated 30 times under the condition that the transport time was 300 s, the silicon wafer with the protective film forming film was correctly held. The number of sheets that could be transported was 30.
When the work of attaching the wafer and the support sheet to the first laminated body of Example 1 was repeated 30 times under the condition that the transport time was 170 s, the silicon wafer with the protective film forming film was correctly held. The number of sheets that could be transported was 30.
When the work of attaching the wafer and the support sheet to the first laminated body of Example 1 was repeated 30 times under the condition that the transport time was 120 s, the silicon wafer with the protective film forming film was correctly held. The number of sheets that could be transported was 29.
When the work of attaching the wafer and the support sheet to the first laminated body of Example 1 was repeated 30 times under the condition that the transport time was 60 s, the silicon wafer with the protective film forming film was correctly held. The number of sheets that could be transported was 28.

A device (Lintec Corporation) that peels off the heavy surface release film of the laminated body sample of Comparative Example 2 and attaches a polished surface of a silicon wafer (200 mm diameter, thickness 350 μm) obtained by polishing the exposed surface of the protective film forming film with # 2000. The table temperature was set to 23 ° C., 60 ° C., and 80 ° C., and the speed was set to 20 mm / sec. At this time, the laminated body sample was also attached to the ring frame for an 8-inch wafer.

<Check for floating>
Evaluation method: As described above, when the first laminate sample of Examples 1 to 8 and Comparative Example 1 and the laminate sample of Comparative Example 2 are attached to a silicon wafer, the protective film forming film / silicon is visually observed. The presence or absence of floating between the wafers and between the protective film forming film / support sheet was confirmed, and Tables 1 and 2 show the evaluation results according to the following criteria.
(Yes): Floating was confirmed visually.
(None): No floating was confirmed visually.

<Check for wrinkles>
Evaluation method: As described above, when the first laminates of Examples 1 to 8 and Comparative Example 1 and the laminate samples of Comparative Example 2 are attached to a silicon wafer, the presence or absence of wrinkles on the substrate is visually observed. The evaluation results are shown in Tables 1 and 2 according to the following criteria.
(Yes): Wrinkles were visually confirmed.
(None): No wrinkles were visually confirmed.

<Phenomenon of take-out when peeling the heavy surface release film>
Evaluation method: As described above, after the first laminates of Examples 1 to 8 and Comparative Example 1 (composed of a light surface release film / protective film forming film / heavy surface release film) are attached to a silicon wafer. When the heavy surface release film was peeled off in the apparatus, it was visually confirmed whether or not the protective film forming film was peeled off together with the heavy surface release film at the end of the wafer. The evaluation results are shown in 2 according to the following criteria.
(Yes): It was visually confirmed that the protective film forming film was peeled off together with the heavy surface release film at the end of the wafer.
(None): At the end of the wafer, it was not visually confirmed that the protective film forming film was peeled off together with the heavy surface release film.

<Phenomenon of cracking of protective film forming film when attaching support sheet>
When the support sheet was attached to the first laminated bodies of Examples 1 to 8 and Comparative Example 1, it was visually confirmed whether or not the protruding portion of the protective film forming film was cracked.

Evaluation method: It was visually confirmed whether or not the protruding portion of the protective film-forming film was cracked, and Tables 1 and 2 show the evaluation results according to the following criteria.
(X): It was visually confirmed that there were two or more places where the protruding portion of the protective film forming film was cracked.
(Δ): It was visually confirmed that there was one place where the protruding part of the protective film forming film was cracked.
(○): It was not visually confirmed that the protruding portion of the protective film forming film was cracked.

<Measurement of elongation at break>
A protective film-forming film having a width of 15 mm, a length of 40 mm, and a thickness of 200 μm was used as a test piece, and the test piece was heated to 23 ° C., a tensile speed of 100 mm / min, and a distance between chucks. The amount of elongation when pulled at 10 mm was measured. The elongation at break was determined from the amount of elongation when the test piece broke.

<Measurement of peeling force of heavy surface release film>
A 25 μm good-adhesive PET (PET25A-4100, manufactured by Toyobo Co., Ltd.) was applied to the protective film-forming film that was exposed by peeling the light-face release film of the composition of the light-face release film / protective film-forming film / heavy-face release film. A good adhesive surface was attached with a thermal laminate (70 ° C., 1 m / min) to prepare a laminate sample. Then, it was cut into a width of 100 mm to prepare a sample for measurement. Next, the back surface of the heavy surface release film of the measurement sample was fixed to the support plate with double-sided tape.

Measuring method: Using a universal tensile tester (manufactured by Shimadzu Corporation, product name "Autograph (registered trademark) AG-IS"), a laminated sample of protective film forming film / good adhesive PET was prepared at 23 ° C. It was peeled from the heavy surface release film at a peeling angle of 180 ° and a peeling speed of 1 m / min, and the load at that time was taken as the peeling force.

When the sample of the first laminate of Example 1 to Example 8, the first laminate of Comparative Example 1, and the laminate sample of Comparative Example 2 were attached to a wafer at a table temperature of less than 80 ° C., the protective film-forming film and the wafer were formed. During the period, floating may be confirmed between the protective film forming film and the support sheet. On the other hand, when the laminate samples of Examples 1 to 8, Comparative Example 1, and Comparative Example 2 were attached to the wafer at a table temperature of 80 ° C., a protective film-forming film was formed. No floating was confirmed between the wafer and the protective film-forming film and the support sheet.
Further, when the laminated body samples of Examples 1 to 8, Comparative Example 1, and Comparative Example 2 were attached to a wafer at a table temperature of 80 ° C., Examples 1 to 8 were attached. 8. No wrinkles were observed on the base material of Comparative Example 1, but wrinkles were observed on the base material of Comparative Example 2.

The kits of Examples 1 to 4, Examples 6 to 8 and Comparative Example 1 are measured at a peeling speed of 1 m / min and a temperature of 23 ° C. between the protective film forming film and the second release film. Since the 180 ° peeling force is 250 mN / 100 mm or less, when the second release film was peeled from the protective film forming film, the protective film forming film was not peeled together with the heavy surface release film. On the other hand, in the kit of Example 5, the 180 ° peeling force described above was larger than 250 mN / 100 mm, so that the protective film forming film was peeled off together with the heavy surface release film.

Since the kits of Examples 1 to 6 and 8 have a breaking elongation of the protective film forming film at 23 ° C. of more than 700%, when the support sheet is attached to the wafer / protective film forming film, the protective film is formed. It was not visually confirmed that the protruding portion of the formed film was cracked.
In the kit of Example 7, since the breaking elongation of the protective film-forming film at 23 ° C. is 730%, when the support sheet is attached to the wafer / protective film-forming film, the protruding portion of the protective film-forming film is cracked. It was visually confirmed that there was one location.
In the kit of Comparative Example 1, since the breaking elongation of the protective film-forming film at 23 ° C. is 700% or less, the protruding portion of the protective film-forming film cracks when the support sheet is attached to the wafer / protective film-forming film. It was visually confirmed that there were two or more places where the film was formed.

From these results, it was clarified that the third laminate can be more preferably produced by the in-line process by using the kits of Examples 1 to 8.

The kit of the present invention can be used in a method for manufacturing a third laminated body, and the third laminated body can be used in manufacturing a semiconductor device with a protective film.

1 ... Kit, 3 ... Composite sheet for forming protective film, 5 ... First laminated body, 6 ... Second laminated body, 7 ... Semiconductor chip with protective film, 8 ... Semiconductor Wafer, 8b ... Back surface of semiconductor wafer, 9 ... Semiconductor chip, 10 ... Support sheet, 10a ... First surface of support sheet, 11 ... Base material, 11a ... Base material First surface, 12 ... Adhesive layer, 12a ... First surface of the adhesive layer, 13 ... Protective film forming film, 13'... Protective film, 13a ... Protective film forming film First surface, 13b ... Second surface of protective film forming film, 14 ... Work, 14a ... Work circuit surface, 14b ... Work back surface, 151 ... First release film (light) Surface release film), 152 ... Second release film (heavy surface release film), 16 ... Adhesive layer for jigs, 17 ... Back grind tape, 18 ... Fixing jigs, 19. .. Third laminate, 19'... Fourth laminate, 20 ... Semiconductor device, 21 ... Semiconductor device with protective film, 70 ... Punching blade

Claims (11)

It is used to support the first laminate in which the first release film, the protective film-forming film, and the second release film are laminated in this order, the work to be protected by the protective film-forming film, and the protective film-forming film. A kit with a support sheet
A kit in which the breaking elongation of the protective film-forming film at 23 ° C. is greater than 700%. The kit according to claim 1, wherein the first laminated body is in the form of a roll. The kit according to claim 1 or 2, wherein the protective film-forming film is thermosetting or energy ray-curable. The kit according to any one of claims 1 to 3, wherein the support sheet is a pressure-sensitive adhesive layer to be attached to the protective film-forming film, which is laminated on a base material. The peeling force between the protective film-forming film and the second release film is larger than the peeling force between the protective film-forming film and the first release film.
The peeling force of 180 ° between the protective film forming film and the second peeling film measured at a peeling speed of 1 m / min and a temperature of 23 ° C. is 250 mN / 100 mm or less, according to claims 1 to 4. The kit described in any one item. A method for producing a third laminate in which a work, the protective film forming film, and the support sheet are laminated in this order, using the kit according to any one of claims 1 to 5 in an in-line process.
The step of peeling the first release film of the first laminated body and
The first laminating step of attaching the exposed surface of the protective film forming film to the work, and
A second laminating step of attaching the support sheet to the surface of the protective film forming film opposite to the exposed surface is included in this order.
A method for manufacturing a third laminated body, wherein the transport distance of the work from the sticking start point of the first laminating step to the sticking completion point of the second laminating step is 7,000 mm or less. A method for producing a third laminate in which a work, the protective film forming film, and the support sheet are laminated in this order, using the kit according to any one of claims 1 to 5 in an in-line process.
The step of peeling the first release film of the first laminated body and
The first laminating step of attaching the exposed surface of the protective film forming film to the work, and
A second laminating step of attaching the support sheet to the surface of the protective film forming film opposite to the exposed surface is included in this order.
A method for producing a third laminated body, wherein the transport time of the work from the start of sticking of the first laminating step to the completion of sticking of the second laminating step is 400 s or less. A method for producing a third laminate in which a work, the protective film forming film, and the support sheet are laminated in this order, using the kit according to any one of claims 1 to 5 in an in-line process.
The step of peeling the first release film of the first laminated body and
The first laminating step of attaching the exposed surface of the protective film forming film to the work, and
A second laminating step of attaching the support sheet to the surface of the protective film forming film opposite to the exposed surface is included in this order.
A method for producing a third laminated body, in which the second laminated body to which the protective film forming film is attached to the work is conveyed one by one between the first laminating step and the second laminating step. The method for producing a third laminated body according to any one of claims 6 to 8, wherein the first laminating step is performed on a wafer table at 80 ° C. or higher. A back grind tape is attached to the surface of the work opposite to the side on which the exposed surface of the protective film forming film is attached, and after the second laminating step, the back grind tape is applied from the work. The method for producing a third laminate according to any one of claims 6 to 9, which comprises a step of peeling. The method for producing a third laminated body according to claim 10, wherein the back grind tape is started to be peeled off from the work in less than 10 minutes from the start of application in the first laminating step.

Images