TW202218868A - Method for manufacturing protective film forming roll which is produced by winding the long strips of the protective film forming film, the first release film provided on one surface of the protective film forming film, and the second release film provided on the other surface of the protective film forming film - Google Patents

Abstract

The present invention provides a method for manufacturing a protective film forming roll which does not easily produce traces. The traces are caused by the winding of the protective film forming film, which will bring traces to the protective film. The manufacturing method of the protective film forming roll includes the following steps: winding the long strips of the protective film forming film, the first release film provided on one surface of the protective film forming film, and the second release film provided on the other surface of the protective film forming film to form a roll; storing the roll at a storage temperature below 10℃ for more than 25 days within 60 days after forming the roll, letting the stripping force for stripping the first release film from the protective film forming film be F1 and the stripping force for stripping the second release film from the protective film forming film be F2, the relationship of F1 > F2 is satisfied, and letting the loss tangent of the protective film forming film at 10DEG C be tan[delta] 10, tan[delta] 10 is less than 1.2.

Description

Manufacturing method of sheet roll for protective film formation

The present invention relates to a method for producing a sheet roll for forming a protective film. In particular, it is related with the manufacturing method of the sheet roll for protective film formation which is hard to generate|occur|produce a trace which originates in the winding of the protective film formation film which gives a trace to a protective film.

In recent years, semiconductor devices have been manufactured using a mounting method called flip-chip bonding. In this mounting method, when mounting a semiconductor wafer having a circuit surface on which convex electrodes such as bumps are formed, the circuit surface side of the semiconductor wafer is inverted (face down) and bonded to the wafer mounting portion. Therefore, the semiconductor device has a structure in which the back side of the semiconductor wafer on which the circuit is not formed is exposed.

Therefore, in order to protect the semiconductor wafer from impact during transportation or the like, a hard protective film made of an organic material is often formed on the back surface side of the semiconductor wafer. Such a protective film is formed by, for example, curing or in a non-cured state after attaching a protective film-forming film to the back surface of a semiconductor wafer.

The protective film forming film constitutes an elongated protective film forming sheet together with a support film supporting the protective film forming film. The elongated sheet is usually wound into a roll before forming a film using a protective film. Furthermore, when a film is formed using a protective film, the long protective film forming sheet unwound from the roll is cut into substantially the same shape as the attached semiconductor wafer, and then attached to the semiconductor wafer.

Patent Document 1 discloses an elongated pressure-sensitive adhesive sheet in which a first sheet and a second sheet are provided on both surfaces of the pressure-sensitive adhesive layer. The adhesive layer can be divided into a punching part and a continuous waste part, and the adhesive layer of the punching part is attached to the back surface of the semiconductor wafer as an adhesive film, for example. [Prior Art Literature] [Patent Literature]

Patent Document 1: International Publication No. 2017/145735

[Technical problem to be solved by the present invention]

The produced long sheet for forming a protective film is fixed to a core using a core fixing tape, and the long sheet for forming a protective film is wound while applying a predetermined tension by a winding device. This formed the sheet roll for protective film formation. As a result, the stress remains in the long sheet for forming a protective film (roll for forming a protective film) after winding, and a winding pressure is generated in the direction toward the core. This winding pressure tends to be large in the protective film forming sheet near the core, that is, in the protective film forming sheet at the start of winding, and small in the protective film forming sheet on the outer peripheral side of the sheet roll.

In addition, due to variations in tension during winding, etc., even in the same sheet roll for forming a protective film, there are places that are strongly squeezed and places that are slightly squeezed, and those that are strongly squeezed for a long time after winding The position may form traces (roll marks) due to winding in the sheet for forming a protective film. In particular, the winding pressure at the position where the winding of the sheet for forming a protective film is started is large, and the variation in winding pressure tends to occur at each position in the width direction after winding. Furthermore, since a level difference occurs due to the thickness of the core fixing tape and the sheet for forming a protective film, the winding pressure caused by the level difference increases, or the variation of the winding pressure in the width direction tends to occur. Therefore, after winding, the sheet for forming a protective film close to the core portion is more likely to generate a roll mark due to being partially strongly pressed than the sheet for forming a protective film on the outer peripheral side of the sheet roll. When such curl marks are generated, curl marks also occur in the protective film forming film constituting the sheet for forming a protective film. As a result, when a protective film forming film is attached to a workpiece and a protective film is formed, curl marks remain and the appearance of the protective film is defective.

However, even if the setting conditions of the winding device are adjusted at the time of forming the sheet roll, it is difficult to completely suppress the curling marks caused by the above-described variation in the winding pressure and the like.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a sheet roll for forming a protective film that is less likely to produce traces due to winding of the protective film forming film that gives traces to the protective film. [Technical means to solve technical problems]

The aspects of the present invention are as follows. [1] A method for producing a sheet roll for forming a protective film, comprising: winding a protective film forming film, a first release film provided on one surface of the protective film forming film, and a The sheet roll formed from the long piece of the second peeling film on the other side is stored at a storage temperature of 10°C or lower for 25 days or more within 60 days after the sheet roll is formed, and a film will be formed from the protective film When the peeling force for peeling the first peeling film from the top is F1, and the peeling force for peeling the second peeling film from the protective film forming film is F2, the relationship of F1>F2 is satisfied, and the protective film forming film at 10° C. When the loss tangent is tanδ ₁₀ , tanδ ₁₀ is 1.2 or less.

[2] The method for producing a sheet roll for forming a protective film according to [1], wherein the step of storing at a storage temperature of 10° C. or lower is started within 10 days after the sheet roll is formed.

[3] The manufacturing method of the sheet roll for protective film formation as described in [1] or [2] whose storage temperature is -10 degreeC or more.

[4] The method for producing a sheet roll for forming a protective film according to any one of [1] to [3], wherein the first release film and/or the second release film is not formed into a film with the protective film The adjoining surfaces are peeled off.

[5] The method for producing a sheet roll for forming a protective film according to any one of [1] to [4], wherein tan δ ₁₀ is 0.04 or more. [Inventive effect]

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the sheet roll for protective film formation which does not easily generate|occur|produce the trace which originates in the winding of the protective film formation film which gives a trace to a protective film can be provided.

Hereinafter, based on a specific embodiment, this invention is demonstrated in detail using drawing.

First, the main terms used in this specification are explained.

The workpiece is a plate-shaped body to be processed by attaching a protective film to form a film. Examples of the workpiece include wafers and panels. Specifically, a semiconductor wafer and a semiconductor panel are mentioned. As a workpiece of a workpiece, for example, a wafer obtained by singulating a wafer can be mentioned. Specifically, a semiconductor wafer obtained by singulating a semiconductor wafer can be exemplified. At this time, the protective film is formed on the back side of the wafer.

The "surface" of the workpiece refers to a surface on which bump electrodes such as circuits and bumps are formed, and the "rear surface" refers to a surface on which circuits and the like are not formed.

In this specification, for example, "(meth)acrylate" is used as a term representing both "acrylate" and "methacrylate", and other similar terms are also the same.

In this specification, the weight ratio of the components constituting each composition is represented by the solid content ratio.

(1. Sheet roll for protective film formation) (1.1 Form of sheet roll for forming protective film) An example of the sheet roll for protective film formation manufactured by the manufacturing method of this embodiment is shown to FIG. 1A. In FIG. 1A , the sheet roll 100 for forming a protective film is a roll formed by winding the long sheet 1 for forming a protective film.

(1.2 Sheet for forming protective film) First, the long strip will be described. The sheet 1 for protective film formation which is a long sheet is used for attaching a protective film forming film to a workpiece. As shown in FIG. 2, the sheet 1 for protective film formation has the structure which arrange|positioned the 1st release film 20 on one main surface 10a of the protective film formation film 10, and arrange|positioned the 2nd release film 30 in the other main surface 10b. Hereinafter, the long sheet 1 may also be referred to as the sheet 1 for forming a protective film.

After the sheet 1 for forming a protective film is wound into a roll, it is stored before use. During storage, the protective film forming film is supported by the first release film and the second release film formed on both main surfaces.

In use, the sheet for forming a protective film is unwound from the roll for forming a protective film, and the protective film forming film is cut into a predetermined shape. After peeling off the second peeling film, a protective film forming film is attached to the back surface of the workpiece, and after peeling of the first peeling film, the protective film is turned into a protective film. The protective film protects the workpiece or the work of the workpiece.

Hereinafter, the protective film forming film, the first peeling film, and the second peeling film constituting the sheet for forming a protective film will be described.

(1.3 Protective film forming film) As described above, the protective film-forming film is formed into a protective film after being attached to the workpiece, and a protective film for protecting the workpiece or the workpiece of the workpiece is formed.

"Protective film formation" refers to a state in which a protective film forming film has sufficient characteristics to protect a workpiece or a workpiece of the workpiece. Specifically, when the protective film-forming film is curable, "protective film-forming" means that the uncured protective film-forming film is made into a cured product. In other words, the protective film-forming film formed into a protective film is a cured product of the protective film-forming film, which is different from the protective film-forming film.

After stacking the workpiece on the curable protective film forming film, by curing the protective film forming film, the protective film can be firmly adhered to the workpiece, and a durable protective film can be formed.

On the other hand, when the protective film forming film does not contain a curable component and is used in an uncured state, the protective film forming film is converted into a protective film when the protective film forming film is attached to the workpiece. In other words, the protective film-forming film formed into a protective film is the same as the protective film-forming film.

When high protective performance is not required, since it is not necessary to harden the protective film forming film, it is easy to use the protective film forming film.

In this embodiment, the protective film forming film is preferably curable. Therefore, the protective film is preferably a cured product. As a hardened|cured material, a thermosetting material and an energy ray hardened|cured material can be illustrated, for example. In this embodiment, it is more preferable that the protective film is a thermosetting product.

Moreover, it is preferable that a protective film-forming film has adhesiveness at normal temperature (23 degreeC), or it exhibits adhesiveness by heating. Thereby, both can be bonded together when stacking a workpiece on the protective film forming film. Therefore, positioning can be accurately performed before curing the protective film-forming film.

The protective film forming film may be composed of one layer (single layer), or may be composed of a plurality of layers of two or more layers. When the protective film forming film has a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the layers constituting the plurality of layers is not particularly limited.

In the present embodiment, the protective film forming film is preferably one layer (single layer). The one-layer protective film-forming film can obtain high precision in thickness and is therefore easy to produce. In addition, when the protective film forming film is composed of a plurality of layers, the adhesion between layers and the stretchability of each layer need to be considered, and there is a risk of peeling from the adherend due to this. When the protective film forming film is one layer, the above-mentioned risk can be reduced, and the degree of freedom of design can be improved.

The thickness of the protective film forming film is not particularly limited, but is preferably less than 100 μm, 70 μm or less, 45 μm or less, or 30 μm or less. By setting the upper limit of the thickness of the protective film forming film to the above-mentioned value, the level difference due to the thickness of the protective film forming sheet at the position where the winding starts can be reduced.

Further, the thickness of the protective film forming film is preferably 5 μm or more, 10 μm or more, and 15 μm or more. By setting the lower limit of the thickness of the protective film forming film to the above-mentioned value, it is easy to obtain the performance of protecting the workpiece as the protective film, and further, in the protective film forming sheet roll, the protective film forming film plays a role of relaxing stress, It is possible to further shorten the length from the core at which the curl marks start to appear.

In addition, the thickness of a protective film forming film means the thickness of the whole protective film forming film. For example, the thickness of the protective film forming film composed of a plurality of layers refers to the total thickness of all the layers forming the protective film forming film.

(1.3.1 Loss tangent of protective film forming film at 10°C) In the present embodiment, the loss tangent (tanδ ₁₀ ) of the protective film forming film at 10°C is 1.2 or less. The loss tangent is defined as "loss modulus/storage modulus", and is a value measured by a dynamic viscoelasticity measuring device in response to a stress applied to an object. By making the loss tangent of the protective film-forming film within the above-mentioned range at 10°C, the components constituting the protective film-forming film become slightly elastic, and the protective film-forming film is not easily deformed, so it has a winding pressure even in the sheet roll. In the case of high, the tendency of curl marks is not easy to appear. Therefore, the present embodiment controls the loss tangent of the protective film forming film at 10°C.

The loss tangent (tanδ ₁₀ ) of the protective film forming film at 10° C. is preferably 1.0 or less, more preferably 0.9 or less, and still more preferably 0.8 or less. Further, the loss tangent (tanδ ₁₀ ) of the protective film forming film at 10° C. is preferably 0.04 or more, more preferably 0.1 or more, still more preferably 0.2 or more, and particularly preferably 0.3 or more. By setting the lower limit of the loss tangent of the protective film forming film at 10°C to the above-mentioned value, the phenomenon that the protective film forming film bent in the sheet roll cracks at 10°C can be prevented.

The loss tangent (tanδ ₁₀ ) of the protective film forming film at 10° C. may be measured by a known method. For example, the protective film-forming film can be made into a sample of a predetermined size, and a dynamic viscoelasticity measuring device can be used to apply strain to the sample at a predetermined frequency in a predetermined temperature range, and measure the elastic modulus. The elastic modulus calculates the loss tangent (tan δ ₁₀ ) at 10°C. The specific measurement method will be described in detail in the following Examples.

(1.4 First release film) The first release film is a film capable of peelably supporting the protective film-forming film. In the present embodiment, the first release film is preferably peeled off from the protective film forming film after the protective film forming film is attached to the workpiece.

The second release film may be composed of one layer (single layer) or two or more layers of base material, and the surface of the base material may be subjected to a release treatment from the viewpoint of controlling the releasability. That is, the surface of the base material may be modified, or a material not derived from the base material may be formed on the surface of the base material.

The thickness of the first release film is not particularly limited, but is preferably 30 μm or more and 100 μm or less. Moreover, it is more preferable that the thickness of a 1st peeling film is 40 micrometers or more, and it is still more preferable that it is 45 micrometers or more. Moreover, as for the thickness of a 1st peeling film, it is more preferable that it is 80 micrometers or less, and it is still more preferable that it is 70 micrometers or less.

By making the lower limit of the thickness of the first release film the above-mentioned value, when a notch reaching a part of the first release film is formed using a dicing blade described later, the dicing blade can be prevented from penetrating the first release film and cutting the first release film. cut off. Furthermore, in the sheet roll for protective film formation, the 1st peeling film plays the role of stress relaxation, and can further shorten the length from the core part at which a roll mark starts to appear.

In addition, before the sheet for forming a protective film is unwound and the protective film forming film is cut out and conveyed to the next step, the sheet for forming a protective film passes through rollers such as guide rollers in the apparatus. At this time, by making the first The upper limit of the thickness of the first release film can be prevented from being peeled off from the first release film. Furthermore, the level difference due to the thickness of the sheet for forming a protective film at the position where the winding starts can be reduced.

In addition, the thickness of a 1st peeling film means the thickness of the whole 1st peeling film. For example, the thickness of the 1st release film which consists of several layers means the total thickness of all the layers which comprise a 1st release film.

In this embodiment, it is preferable that the 1st release film has a base material and a 1st release agent layer. By having the first release agent layer, it becomes easy to control the physical properties of the surface on which the first release agent layer is formed in the first release film.

In addition, in this embodiment, in the sheet for protective film forming, the peeling force for peeling the first release film from the protective film forming film is set to F1, and the peeling force for peeling the second peeling film from the protective film forming film described later is used. When set to F2, F1 and F2 satisfy the relationship of F1>F2. By satisfying this relationship, when the second peeling film is removed from the sheet for forming a protective film, the protective film forming film 10 that should remain is not removed together with the second peeling film, and the protective film forming film 10 is easily left on the first peeling film. a release film.

Therefore, the first release film is a heavy release film, and the second release film is a light release film.

In the present embodiment, F1 and F2 are load values measured using a tensile tester. The specific measurement method will be described in detail in the following Examples.

(1.4.1 Substrate) The base material of the first release film is not particularly limited as long as it is a material that can support the protective film forming film before the protective film forming film is attached to the workpiece. resin film”).

As specific examples of the resin film, polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, polyterephthalene films can be used Ethylene formate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene-(methyl) ) acrylic copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. In addition, cross-linked films of these films can also be used. Furthermore, it may be a laminated film of these films. In the present embodiment, a polyethylene terephthalate film is preferable from the viewpoints of environmental safety, cost, and the like, and from the viewpoint of suppressing winding up accompanying the extension of the base material.

The base material may contain various additives such as colorants, flame retardants, plasticizers, antistatic agents, lubricants, and fillers in the resin film.

The thickness of the base material is not particularly limited within the range of the thickness of the first release film that can function appropriately in each step of using the sheet for forming a protective film. The thickness of the base material is preferably 30 μm or more and 100 μm or less. Further, the thickness of the base material is more preferably 40 μm or more, and further preferably 45 μm or more. In addition, the thickness of the base material is more preferably 80 μm or less, and further preferably 70 μm or less.

(1.4.2 The first release agent layer) The first release agent layer imparts releasability to the first release film from the protective film-forming film. The first release agent layer is not particularly limited as long as it is composed of a material that can impart releasability. In this embodiment, a 1st release agent layer can be obtained by hardening the composition for 1st release agent layers containing a mold release agent.

In the first release film, it is preferable to form the first release agent layer directly on the surface of the base material. By directly forming the first release agent layer on the surface of the base material, the production of the first release film becomes easy, so that cost reduction can be achieved.

The thickness of the first release agent layer is not particularly limited, but is preferably 30 nm or more and 200 nm or less. In addition, the thickness of the first release agent layer is more preferably 50 nm or more, and further preferably 80 nm or more. Further, the thickness of the first release agent layer is more preferably 180 nm or less.

By making the thickness of a 1st release agent layer into the said range, when sticking a protective film forming film to a workpiece|work, stable release performance can be exhibited.

Moreover, in this embodiment, it is preferable to form a 1st release agent layer on the surface of the opposite side in addition to forming a 1st release agent layer on the surface of the protective film formation film side of a 1st release film. That is, as shown in FIG. 3 , in the sheet 1 for forming a protective film, the first release film 20 has a base material 21 and first release agent layers 22 and 23 formed on both main surfaces of the base material 21 . The main surface 20b of the first release film (the main surface 20b of the first release agent layer 22) is in contact with the main surface 10a of the protective film forming film. The first release agent layer 22 and the first release agent layer 23 may be composed of the same composition or may be composed of different compositions.

In the sheet roll, since the long sheets 1 are stacked in the radial direction, the surface 20a of the first release film 20 not in contact with the protective film forming film 10 and the surface 20a of the second release film 30 not in contact with the protective film forming film 10 The faces 30b are in contact with each other. Therefore, in the first release film 20, by subjecting the surface 20a that is not in contact with the protective film forming film 10 to a release treatment (by forming the first release agent layer 23), the long pieces in contact with each other are easily slid, so that it is possible to Stabilization of the winding pressure described later is promoted.

(1.5 Second release film) The second release film is a film capable of peelably supporting the protective film-forming film. In the present embodiment, it is preferable to peel the second release film from the protective film forming film before attaching the protective film forming film to the workpiece.

Like the first release film, the second release film may be composed of one layer (single layer) or two or more layers of substrates, and the surface of the substrate may be subjected to release treatment from the viewpoint of controlling the releasability. That is, the surface of the base material may be modified, or a material not derived from the base material may be formed on the surface of the base material.

The thickness of the second release film is not particularly limited, but is preferably 10 μm or more and 75 μm or less. Moreover, as for the thickness of a 2nd peeling film, 18 micrometers or more are more preferable, and 24 micrometers or more are still more preferable. Moreover, as for the thickness of a 2nd peeling film, it is more preferable that it is 60 micrometers or less, and it is still more preferable that it is 45 micrometers or less. The thickness of the second release film is preferably less than or equal to the thickness of the first release film, and more preferably smaller than the thickness of the first release film, from the viewpoint of making the peeling force F2 and the peeling force F1 to satisfy the above-mentioned F1>F2.

In addition, the thickness of a 2nd peeling film means the thickness of the whole 2nd peeling film. For example, the thickness of the 2nd peeling film which consists of several layers means the total thickness of all the layers which comprise a 2nd peeling film.

In this embodiment, it is preferable that the second release film has a base material and a second release agent layer. By having the second release agent layer, it becomes easy to control the physical properties of the surface on which the second release agent layer is formed in the second release film.

(1.5.1 Substrate) The base material of the second release film can be appropriately selected from the materials exemplified as the base material of the first release film.

(1.5.2 Second release agent layer) When the second release film has a second release agent layer, the second release agent layer is not particularly limited as long as the second release agent layer is made of a material capable of imparting releasability. For example, like a 1st release agent layer, a 2nd release agent layer can be obtained by hardening the composition for 2nd release agent layers containing a silicon-oxygen (silicone) type mold release agent.

Like the first release film, in the second release film, it is preferable to form the second release agent layer directly on the surface of the base material. By forming the second release agent layer directly on the surface of the base material, production of the second release film becomes easy, and thus cost reduction can be achieved.

Moreover, in this embodiment, the 2nd release agent layer is formed in the surface of the protective film formation film side of a 2nd release film. That is, as shown in FIG. 3, in the sheet 1 for protective film formation, the 2nd release film 30 has the base material 31, and the 2nd release agent layer 32 formed on the surface of the base material 31 on the protective film formation film side. The main surface 30 a of the second release film 30 (the main surface 30 a of the second release agent layer 32 ) is in contact with the main surface 10 b of the protective film forming film 10 . Moreover, in addition to forming a 2nd release agent layer on the surface 30b of the protective film formation film side of the 2nd release film 30, you may form a 2nd release agent layer on the surface 30b of the opposite side.

In addition, when forming the second release agent layer on both main surfaces of the base material, the second release agent layer can be formed by applying a coating agent containing a composition for a second release agent layer described later on both main surfaces of the base material. For the release agent layer, after applying the coating agent containing the composition for the second release agent layer to one main surface of the base material, the base material may be wound to form a roll, and the composition for the second release agent layer may be used. The phenomenon (transfer phenomenon) in which the components of the coating agent are transferred from the main surface on which the coating agent is applied to the main surface on which the coating agent is not applied (transfer phenomenon), and a second release agent layer is formed on the main surface on which the coating agent is not applied.

(2. Manufacturing method of the sheet roll for protective film formation) In the manufacturing method of the sheet roll for protective film formation of this embodiment, first, the length in the longitudinal direction of the sheet for protective film formation having the above-mentioned protective film formation film, the first release film, and the second release film is manufactured to be much longer than A long piece of length in the short side direction. The long sheet may be produced by a known method, and the specific method will be described later.

Then, while cutting both sides in the width direction of the long sheet according to the size of the workpiece to which the protective film forming film is to be attached to adjust the size in the width direction, a predetermined tension is applied by a winding device to wind up, thereby producing a protective film. Sheet rolls for film formation.

In addition, when the width of the workpiece is 150 mm, the length in the width direction after cutting is preferably in the range of 155 to 194 mm, and when the width of the workpiece is 200 mm, the length in the width direction after cutting is preferably in the range of 205 to 250 mm. When the width is 300 mm, the length in the width direction after cutting is preferably in the range of 305 to 350 mm, and when the width of the workpiece is 450 mm, the length in the width direction after cutting is preferably in the range of 455 to 500 mm.

As shown in FIG. 1B , the long sheet 1 is fixed to the core 70 via a fixing tool 80 such as a core fixing tape, and then the long sheet 1 is wound by applying a predetermined tension to the long sheet 1 by the winding device. On the core portion 70, the above-described sheet roll 100 is thus formed. As described above, in the finished sheet roll, there is a variation in the winding pressure, and especially in the long sheet close to the core, the position where the sheet is strongly squeezed tends to form a protective film that gives traces to the protective film Roll marks of the film are formed.

On the other hand, it is presumed that after the sheet roll is formed, that is, after the winding is completed, the winding pressure at the position where the winding pressure is high gradually decreases over time, and approaches the winding pressure at the position where the winding pressure is low. In other words, it is presumed that the variation in the winding pressure is eliminated with the passage of time, and the winding pressure in the sheet roll is stabilized (averaged). Therefore, although the deviation of the winding pressure in the sheet roll is finally largely eliminated, the winding marks formed before the deviation of the winding pressure is eliminated will remain in the protective film-forming film even after the deviation of the winding pressure is eliminated. middle.

However, when the loss tangent of the protective film-forming film is low and the protective film-forming film is not easily deformed, even if there is a variation in the winding pressure and there is a strongly squeezed position, the protective film-forming film is not easily formed with curling marks. Moreover, when the temperature becomes low, it becomes easy to maintain the loss tangent of a protective film formation film low. Further, as described above, the winding pressure in the sheet roll tends to stabilize over time.

(2.1 Storage Procedure) Therefore, in the present embodiment, the sheet roll just wound is stored for a predetermined time until the winding pressure is stabilized while maintaining the loss tangent of the protective film forming film within the above-mentioned range.

Specifically, the manufacturing method of the sheet roll for protective film formation of this embodiment has a process of forming the protective film forming film having a loss tangent (tanδ ₁₀ ) of 1.2 or less from the protective film forming film at 10° C. After the sheet roll, the sheet roll is stored for 60 days, and the sheet roll is stored at a storage temperature of 10° C. or lower during a period of 25 days or more of the 60 days.

For a sheet roll having a protective film-forming film whose loss tangent (tanδ ₁₀ ) of the protective film-forming film at 10° C. is 1.2 or less, the sheet roll is stored at a temperature of 10° C. or lower until the winding pressure of the sheet roll is stabilized, The protective film-forming film easily achieves the loss tangent within the above-mentioned range, so that the formation of curl marks on the protective-film-forming film in the sheet roll can be suppressed.

In addition, the period during which the sheet roll is stored at a storage temperature of 10° C. or lower is preferably 30 days or more, 35 days or more, 40 days or more, or 45 days or more. On the other hand, the period is preferably 60 days or less and 59 days or less.

Further, the storage at a storage temperature of 10° C. or lower is preferably started within 10 days, more preferably within 7 days, and even more preferably within 4 days after the sheet roll is formed. In the sheet roll just wound, since there is a tendency that the variation in the winding pressure is large, by keeping the loss tangent of the protective film forming film low with certainty, it is possible to further suppress the increase in the protective film forming film in the sheet roll. formation of curl marks.

Further, the storage temperature is preferably -10°C or higher, more preferably -5°C or higher, and further preferably 0°C or higher. By making the lower limit of the storage temperature the above-mentioned value, the elastic modulus of the protective film-forming film can be suppressed from becoming too high, and the gap between the protective film-forming film and the release film, especially between the protective film-forming film and the second film can be suppressed. Peeling occurs between the release films.

Through the above-mentioned storage process, the sheet roll for forming a protective film of the present embodiment can be obtained. Even if the sheet for forming a protective film is unwound from the roll for forming a sheet for forming a protective film by storing the sheet for forming a protective film whose loss tangent tanδ ₁₀ at 10°C is 1.2 or less in the above-mentioned storage procedure, Formation of curl marks on the protective film forming film up to the protective film forming sheet on the core portion side can also be suppressed. Therefore, the appearance defect of a protective film is suppressed, and the sheet roll for protective film formation of this embodiment can be used up without waste.

(2.2 Manufacturing method of long strip) About the manufacturing method of the sheet roll for protective film formation of this embodiment, what is necessary is just to manufacture the elongate sheet|seat which has the said structure by a well-known method. In this embodiment, the case where a 1st release film has the above-mentioned base material and a 1st release agent layer, and a 2nd release film has the above-mentioned base material and a 2nd release agent layer is demonstrated.

The protective film forming film is formed using the composition for a protective film forming film, the first releasing agent layer is formed using the composition for the first releasing agent layer, and the second releasing agent layer is formed using the composition for the second releasing agent layer.

Hereinafter, the composition for protective film forming films, the composition for 1st release agent layers, and the composition for 2nd release agent layers are demonstrated.

(2.2.1 Composition for forming a protective film) The composition of the protective film forming film is not particularly limited as long as the protective film forming film has the above-mentioned physical properties. In this embodiment, it is preferable that the composition (composition for protective film forming films) which comprises a protective film forming film is a resin composition containing at least a polymer component (A), a curable component (B), and a filler (E). The polymer component can be regarded as a component formed by a polymerization reaction of a polymerizable compound. In addition, a curable component is a component which can undergo a curing (polymerization) reaction. In addition, the polymerization reaction in the present invention also includes a polycondensation reaction.

In addition, the component contained in the polymer component may also be a curable component. In the present embodiment, when the composition for a protective film-forming film contains such a component that is both a polymer component and a curable component, it is considered that the composition for a protective film-forming film contains both the polymer component and the curable component.

(2.2.1.1 Polymer composition) The polymer component (A) imparts film formability (film-forming properties) to the protective film-forming film, and at the same time provides moderate tackiness, so that the protective film-forming film can be reliably adhered to the workpiece uniformly. The weight average molecular weight of the polymer component is usually in the range of 50,000 to 2,000,000, preferably 100,000 to 1,500,000, and particularly preferably 200,000 to 1,000,000. As such a polymer component, an acrylic resin, a urethane resin, a phenoxy resin, a silicone resin, a saturated polyester resin, etc. can be used, for example, and an acrylic resin is used especially preferably.

In addition, in this specification, unless otherwise specified, "weight average molecular weight" means the polystyrene conversion value measured by gel permeation chromatography (GPC). Measurement based on this method can be performed, for example, by connecting the high-speed column "TSK guard column H _XL -H", "TSK Gel GMH XL", "TSK Gel GMH _XL ", For an apparatus made of "TSK Gel G2000 H _XL " (all of which are manufactured by TOSOH CORPORATION), the detector was a differential refractometer under the conditions of column temperature: 40°C and liquid feed rate: 1.0 mL/min.

As an acrylic resin, the (meth)acrylate copolymer which consists of a (meth)acrylate monomer and the structural unit derived from a (meth)acrylic acid derivative is mentioned, for example. Here, as a (meth)acrylate monomer, the C1-C18 alkyl (meth)acrylate of an alkyl group is mentioned preferably, and specifically, methyl (meth)acrylate is mentioned. ester, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc. Moreover, as a (meth)acrylic acid derivative, (meth)acrylic acid, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc. are mentioned, for example.

In this embodiment, a glycidyl group is preferably introduced into the acrylic resin using glycidyl methacrylate or the like. The mutual solubility of the glycidyl group-introduced acrylic resin and the epoxy resin as a thermosetting component described later is improved, and there is a tendency that a protective film-forming film having stable performance is easily obtained. In addition, in this embodiment, in order to control the adhesiveness to a workpiece or the physical properties of the adhesive, it is preferable to introduce a hydroxyl group into the acrylic resin using hydroxyethyl acrylate or the like.

The glass transition temperature of the acrylic resin is preferably -70 to 40°C, -35 to 35°C, -20 to 30°C, -10 to 25°C, and -5 to 20°C. By making the lower limit of the glass transition temperature of the acrylic resin the above-mentioned value, it becomes easy to reduce the tanδ ₁₀ of the protective film-forming film. In addition, by setting the upper limit of the glass transition temperature of the acrylic resin to the above-mentioned value, the viscosity of the protective film-forming film can be appropriately improved, the adhesion between the protective film-forming film and the workpiece, and the adhesion between the protective film and the workpiece can be appropriately improved. force.

式中，Tg為丙烯酸樹脂的玻璃轉化溫度；m為2以上的整數；Tgk為單體m的均聚物的玻璃轉化溫度；Wk為丙烯酸樹脂中的由單體m衍生的結構單元m的質量分數，其中，Wk滿足下述式。 [數學式2]

式中，m及Wk與所述m及Wk相同。 When the acrylic resin has m types (m is an integer of 2 or more) structural units, the glass transition temperature of the acrylic resin can be calculated as follows. That is, when m types of monomers from which the structural unit in the acrylic resin is derived are sequentially assigned any non-repeating number from 1 to m, and named "monomer m", the glass transition temperature (Tg) of the acrylic resin It can be calculated using the Fox formula shown below. [Mathematical formula 1]

In the formula, Tg is the glass transition temperature of the acrylic resin; m is an integer of 2 or more; Tgk is the glass transition temperature of the homopolymer of the monomer m; Wk is the mass of the structural unit m derived from the monomer m in the acrylic resin score, where Wk satisfies the following formula. [Mathematical formula 2]

In the formula, m and Wk are the same as the above-mentioned m and Wk.

As Tgk, the value described in Polymer Data Handbook, Adhesion Handbook, Polymer Handbook, or the like can be used. For example, a homopolymer of methyl acrylate has a Tgk of 10°C, a homopolymer of n-butyl acrylate has a Tgk of -54°C, a homopolymer of methyl methacrylate has a Tgk of 105°C, and 2-hydroxyethyl acrylate has a Tgk of 105°C. The Tgk of the ester homopolymer was -15°C, the Tgk of the glycidyl methacrylate homopolymer was 41°C, and the Tgk of 2-ethylhexyl acrylate was -70°C.

When the total weight of the composition for forming a protective film is set to 100 parts by mass, the content of the polymer component is preferably 5 to 80 parts by mass, 8 to 70 parts by mass, 10 to 60 parts by mass, 12 to 55 parts by mass, 14 parts by mass ~50 parts by mass, 15-45 parts by mass. By making the content of the polymer component within the above-mentioned range, the viscosity of the protective film-forming film can be appropriately increased, and the adhesive force between the protective film-forming film and the workpiece can be appropriately increased. In addition, there is a tendency to easily suppress the occurrence of curl marks.

(2.2.1.2 Thermosetting components) The curable component (B) forms a hard protective film by curing the protective film-forming film. As the curable component, a thermosetting component, an energy ray-curable component, or a mixture thereof can be used. When it is hardened by irradiating an energy ray, since the protective film forming film contains the filler, coloring material, etc. which are mentioned later, the light transmittance falls. Therefore, for example, when the thickness of the protective film forming film increases, the energy ray curing tends to become insufficient.

On the other hand, a thermosetting protective film-forming film can be sufficiently cured by heating even if its thickness is increased, so that a protective film with high protective performance can be formed. Moreover, by using common heating equipment, such as a heating oven, many protective film forming films can be heated collectively, and can be thermally cured.

Therefore, in this embodiment, the curable component is desirably thermosetting. That is, the protective film forming film is preferably thermosetting.

Whether or not the protective film forming film is thermosetting can be determined as follows. First, the protective film-forming film at normal temperature (23° C.) is heated to a temperature exceeding normal temperature, and then cooled to normal temperature to prepare a protective film-forming film after heating and cooling. Next, when the hardness of the protective film-forming film after heating and cooling was compared with the hardness of the protective-film-forming film before heating at the same temperature, the case where the protective film-forming film after heating and cooling was harder was judged to be the protection Film-forming films are thermosetting.

As the thermosetting component, for example, epoxy resins, thermosetting polyimide resins, unsaturated polyester resins, and mixtures thereof are preferably used. The thermosetting polyimide resin is a general term for a polyimide precursor and a thermosetting polyimide that can be thermally cured to form a polyimide resin.

The epoxy resin, which is a thermosetting component, has a property of forming a three-dimensional network structure and forming a strong coating when heated. As such an epoxy resin, well-known various epoxy resins can be used. In this embodiment, the molecular weight (formula weight) of the epoxy resin is preferably 300 or more and less than 50,000, 300 or more and less than 10,000, 300 or more and less than 5,000, 300 or more and less than 3,000. In addition, the epoxy equivalent of the epoxy resin is preferably 50 to 5000 g/eq, more preferably 100 to 2000 g/eq, still more preferably 150 to 1000 g/eq.

Specific examples of the epoxy resins include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, and cresol novolac; butanediol; , glycidyl ethers of alcohols such as polyethylene glycol and polypropylene glycol; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; substituted aniline isocyanuric acid with glycidyl group Glycidyl-type or alkyl-glycidyl-type epoxy resins of ester (aniline isocyanurate) and other active hydrogen bonded to nitrogen atoms; vinylcyclohexane diepoxide, 3,4-epoxycyclohexyl Methyl-3,4-bicyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane etc., so-called alicyclic epoxides which introduce an epoxy group by, for example, oxidizing a carbon-carbon double bond in the molecule. In addition, epoxy resins having a biphenyl skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, and the like can also be used.

When a thermosetting component is used as a curable component (B), it is preferable to use a curing agent (C) together as an auxiliary agent. As the curing agent for epoxy resins, a thermally active latent epoxy resin curing agent is preferable. "Thermally active latent epoxy resin curing agent" refers to a curing agent of a type that does not easily react with epoxy resins at room temperature (23°C), and is activated by heating above a certain temperature to react with epoxy resins. For the activation method of thermally active latent epoxy resin curing agent, there are: a method of generating active species (anions, cations) by chemical reaction based on heating; stably dispersed in epoxy resin near normal temperature, and reacted with ring at high temperature Oxygen resins are mutually soluble - a method of dissolving and starting a curing reaction; a method of starting the curing reaction after dissolving a molecular sieve-encapsulated type curing agent at a high temperature; a method based on microcapsules, etc.

Among the exemplified methods, a method of stably dispersing in the epoxy resin at the vicinity of normal temperature, and mutually dissolving and dissolving with the epoxy resin at a high temperature to initiate a curing reaction is preferable.

Specific examples of the thermally active latent epoxy resin curing agent include various onium salts, diacid dihydrazide compounds, dicyandiamide, amine adduct curing agents, imidazole compounds and other high melting point active hydrogen compounds. Wait. These thermally active latent epoxy resin curing agents may be used alone or in combination of two or more. Dicyandiamide is particularly preferred in this embodiment.

Moreover, as a hardening|curing agent for epoxy resins, a phenol resin is also preferable. As the phenol resin, polycondensates of phenols and aldehydes such as alkylphenols, polyhydric phenols, and naphthols and the like can be used without particular limitation. Specifically, phenol novolac resin, o-cresol novolak resin, p-cresol novolac resin, t-butylphenol novolak resin, dicyclopentadiene cresol resin, poly-p-vinylphenol resin, bisphenol can be used A-type novolak resins, or their modifications, and the like.

The phenolic hydroxyl group contained in these phenol resins can be easily added and reacted with the epoxy group of the epoxy resin by heating to form a cured product with high impact resistance.

The content of the curing agent (C) is preferably 0.01 to 30 parts by mass, 0.1 to 20 parts by mass, 0.2 to 15 parts by mass, and 0.3 to 10 parts by mass relative to 100 parts by mass of the epoxy resin. By making the range of content of a hardening|curing agent (C) into the said range, it becomes easy to obtain the performance which protects a workpiece|work as a protective film.

When using dicyandiamide as a curing agent (C), it is more preferable to use a curing accelerator (D) together. As the curing accelerator, for example, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl- Imidazoles such as 4-methyl-5-hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are substituted by groups other than hydrogen atoms). Among them, 2-phenyl-4,5-dimethylolimidazole is particularly preferable.

The content of the curing accelerator is preferably 0.01 to 30 parts by mass, 0.1 to 20 parts by mass, 0.2 to 15 parts by mass, and 0.3 to 10 parts by mass relative to 100 parts by mass of the epoxy resin. By making content of a hardening accelerator (D) into the said range, it becomes easy to obtain the performance which protects a workpiece as a protective film.

When the total weight of the composition for forming a protective film is set to 100 parts by mass, the total content of the thermosetting component and the curing agent is preferably 3 to 80 parts by mass, 5 to 60 parts by mass, 7 to 50 parts by mass, and 9 to 40 parts by mass parts, 10 to 30 parts by mass. When the thermosetting component and the curing agent are blended in such a ratio, the performance of protecting the workpiece can be easily obtained as a protective film.

(2.2.1.3 Energy ray curable components) When the curable component (B) is an energy ray curable component, the energy ray curable component is preferably uncured, preferably has adhesiveness, and more preferably has uncured and adhesiveness.

The energy ray-curable component is a component that is cured by irradiation with an energy ray, and is a component for imparting film-forming properties, flexibility, and the like to the protective film-forming film.

As the energy ray-curable component, for example, a compound having an energy ray-curable group is preferable. As such a compound, a well-known compound is mentioned.

(2.2.1.4 Filling material) By making the protective film forming film contain the filler (E), the adjustment of the thermal expansion coefficient of the protective film obtained by converting the protective film forming film into a protective film becomes easy. By making the thermal expansion coefficient close to the thermal expansion coefficient of the workpiece, the adhesion reliability with the workpiece is further improved. Moreover, by making a protective film forming film contain a filler (E), a hard protective film can be easily obtained, the performance of protecting a workpiece can be obtained, and the moisture absorption rate of a protective film can be reduced.

The filler (E) may be either an organic filler or an inorganic filler, but an inorganic filler is preferable from the viewpoint of shape stability at high temperatures such as 260°C.

Examples of preferred inorganic fillers include powders of silica, alumina, talc, calcium carbonate, red iron oxide, silicon carbide, boron nitride, etc.; beads formed by spheroidizing these inorganic fillers; Surface modifiers of fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among them, silica and surface-modified silica are preferred. The surface-modified silica is preferably surface-modified with a coupling agent, and more preferably surface-modified with a silane coupling agent.

The average particle diameter of the filler is preferably 0.02 to 10 μm, 0.05 to 5 μm, and 0.10 to 3 μm.

By making the range of the average particle diameter of a filler into the said range, the handleability of the composition for protective film forming films becomes favorable. As a result, the composition for a protective film-forming film and the quality of the protective film-forming film are easily stabilized.

In addition, unless otherwise specified, the "average particle diameter" in this specification refers to the value of the particle diameter (D50) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method.

The content of the filler when the total weight of the composition for forming a protective film is 100 parts by mass is preferably 15 to 80 parts by mass, 30 to 75 parts by mass, 40 to 70 parts by mass, and 45 to 65 parts by mass.

By making the lower limit of the content of the filler into the above-mentioned value, there is a tendency that tan δ ₁₀ of the protective film-forming film is easily reduced. Moreover, by making the upper limit of content of a filler to the said value, the adhesive force of a protective film forming film and a workpiece|work improves, and there exists a tendency for the adhesive force of a protective film and a workpiece|work to improve moderately.

(2.2.1.5 Coupling agent) The protective film-forming film preferably contains a coupling agent (F). By containing the coupling agent, after curing of the protective film-forming film, the adhesion between the protective film and the workpiece can be improved without impairing the heat resistance of the protective film, and at the same time, the water resistance (moisture and heat resistance) can be improved. As the coupling agent, a silane coupling agent is preferable from the viewpoint of its versatility and cost advantage.

Examples of the silane coupling agent include γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl ) ethyltrimethoxysilane, γ-(methacryloyloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyl Trimethoxysilane, N-6-(aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethyl Oxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane , Methyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, imidazole silane, etc. These silane coupling agents may be used alone or in combination of two or more.

(2.2.1.6 Colorants) The protective film-forming film preferably contains a colorant (G). Thereby, since the back surface of the workpiece such as a wafer can be shielded, various electromagnetic waves generated in the electronic device can be blocked, and malfunction of the workpiece such as a wafer can be reduced.

As a coloring agent (G), well-known pigments, such as an inorganic type pigment, an organic type pigment, and an organic type dye, can be used, for example. In this embodiment, inorganic pigments are preferred.

Examples of inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO ( Indium tin oxide) dyes, ATO (antimony tin oxide) dyes, etc. Among them, carbon black is particularly preferably used. In the case of carbon black, electromagnetic waves in a wide wavelength range can be blocked.

The blending amount of the colorant (especially carbon black) in the protective film-forming film may vary depending on the thickness of the protective film-forming film. For example, when the thickness of the protective film-forming film is 20 μm, the amount of In terms of mass, the blending amount of the colorant is preferably 0.01 to 10% by mass, 0.04 to 7% by mass, and 0.07 to 4% by mass. By making the compounding quantity of a coloring agent into the said range, it exists in the tendency to make the trace of a protective film by the roll mark of the sheet roll for protective film formation inconspicuous in appearance.

The average particle diameter of the colorant (especially carbon black) is preferably 1 to 500 nm, particularly preferably 3 to 100 nm, and further preferably 5 to 50 nm. When the average particle diameter of the colorant is within the above-mentioned range, the light transmittance can be easily controlled within a desired range.

(2.2.1.7 Other additives) The composition for forming a protective film may further contain, for example, a photopolymerization initiator, a crosslinking agent, a plasticizer, an antistatic agent, an antioxidant, a getter, a tackifier, a Release agent etc. as other additives.

(2.2.2 Composition for the first release agent layer) In this embodiment, the composition for the first release agent layer may contain, for example, an alkyd-based mold release agent, a silicone-based mold release agent, a fluorine-based mold release agent, an unsaturated polyester-based mold release agent, and a polyolefin-based mold release agent , Wax-based mold release agents, which preferably contain silicone-based mold release agents. When the composition for the first release agent layer contains a silicone-based release agent, it is preferable to include a silicone-based release agent and a heavy release additive.

(2.2.2.1 Silicon oxide mold release agent) As the silicone-based mold release agent, a silicone mold release agent in which silicone having dimethylpolysiloxane as a basic skeleton is blended can be used.

When the total weight of the composition for the first release agent layer (excluding the catalyst described later) is 100 parts by mass, the content of the silicon oxide formed from dimethylpolysiloxane is preferably less than 100 parts by mass and less than 90 parts by mass , less than 80 parts by mass, less than 70 parts by mass.

The silicone may be any of addition reaction type, polycondensation reaction type, and energy ray curing type such as ultraviolet curing type and electron beam curing type, and is preferably addition reaction type silicone. The addition reaction type siloxane has high reactivity and excellent productivity, and at the same time, compared with the polycondensation reaction type, it has advantages such as less change in the peeling force after manufacture and no curing shrinkage.

Specific examples of addition-reaction-type siloxanes include those having 2 to 10 carbon atoms such as vinyl, allyl, propenyl, and hexenyl groups at the terminal and/or side chain of the molecule. Alkenyl organopolysiloxanes.

When such an addition reaction type silica is used, it is preferable to use a crosslinking agent and a catalyst together.

As a crosslinking agent, the organopolysiloxane which has at least 2 hydrogen atoms couple|bonded with a silicon atom in 1 molecule is mentioned, for example.

Specific examples of the crosslinking agent include dimethylhydrosiloxy-terminated dimethylsiloxane-methylhydrosiloxane copolymer, trimethylsiloxy-terminated dimethyl Siloxane-methylhydrosiloxane copolymer, trimethylsiloxy-terminated methylhydropolysiloxane, poly(hydrosilsesquioxane), etc.

Examples of catalysts include particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, and platinum group metals such as rhodium. compounds, etc.

By using the said catalyst, the hardening reaction of the composition for 1st release agent layers can progress more efficiently.

From the viewpoint of making the peeling force F1 within the above-mentioned range, the content of the silicone-based mold release agent when the total weight of the composition for the first release agent layer (excluding the catalyst) is 100 parts by mass is preferably 30 to 100 parts by mass, 50 to 100 parts by mass.

(2.2.2.2 Heavy Peel Additives) The heavy peeling additive is used to increase the peeling force F1 for peeling the first peeling film from the protective film-forming film. Examples of the heavy release additive include siloxanes such as silicone resins and silane coupling agents, and among them, silicone resins are preferably used.

As the silicone resin, it is preferable to use, for example, an MQ resin containing an M unit as a monofunctional siloxane unit [R ₃ SiO _1/2 ] and a Q unit as a tetrafunctional siloxane unit [SiO _4/2 ] . In addition, the three Rs in the M unit each independently represent a hydrogen atom, a hydroxyl group, or an organic group. From the viewpoint of easy inhibition of silicon-oxygen transfer, one or more of the three Rs in the M unit is preferably a hydroxyl group or a vinyl group, and more preferably a vinyl group.

When the total weight of the composition for the first release agent layer (excluding the catalyst) is 100 parts by mass, the content of the heavy release additive is preferably 0 to 50 parts by mass, 5 to 45 parts by mass, and 10 to 40 parts by mass.

In addition, when forming the first release agent layer on both main surfaces of the base material, the first release agent layer can be formed by applying a coating agent containing the composition for the first release agent layer to be described later on both main surfaces of the base material. For the release agent layer, after applying the coating agent containing the composition for the first release agent layer to one main surface of the base material, the base material may be wound to form a roll, and the composition for the first release agent layer may be used. A phenomenon (transfer phenomenon) in which the components of the coating agent are transferred from the main surface on which the coating agent is applied to the main surface on which the coating agent is not applied (transfer phenomenon), and a first release agent layer is formed on the main surface on which the coating agent is not applied.

In the first release film, for example, whether or not the base material has undergone a release treatment can be determined as follows. When the first release agent layer contains the above-mentioned silicone-based release agent, the surface analysis of the two main surfaces of the first release film is performed by X-ray photoelectron spectroscopy (XPS), and the ratio of silicon atoms is calculated from the obtained spectrum, If it is a predetermined value or more, it will be judged that a peeling process has been performed. The specific measurement method will be described in detail in the following Examples.

Moreover, when the base material consists of a polyethylene terephthalate film, the contact angle of water was measured with respect to both main surfaces of a 1st peeling film, and it was judged that the peeling process was performed when the contact angle was a predetermined value or more. The specific measurement method will be described in detail in the following Examples.

(2.2.3 Composition for the second release agent layer) The composition for the second release agent layer can be selected from the materials exemplified in the composition for the first release agent layer as long as the relationship between F1 and F2 described above is satisfied. Among them, it is preferable that the content of the material exemplified as the heavy release additive is less than the content in the composition for the first release agent layer, or not included.

Moreover, in the range which does not impair the effect of this invention, the composition for 1st release agent layers and the composition for 2nd release agent layers may contain the normally used additive in a release agent layer. As such an additive, a dye, a dispersing agent, etc. are mentioned.

In addition, from the viewpoint of adjusting the peeling force to be low, and from the viewpoint of making it easier to form the release agent layer utilizing the above-mentioned transfer phenomenon, the composition for the release agent layer (the composition for the first release agent layer and the second release agent layer) Silicone oil is added to the release agent layer composition).

(2.2.4 Manufacturing steps of long strips) When producing a long sheet, first, the above-mentioned composition for protective film forming films, the composition for 1st release agent layers, and the composition for 2nd release agent layers are prepared. In the present embodiment, it is preferable to prepare a coating agent prepared by diluting the composition for protective film-forming films and the composition for releasing agent layers containing each of the above components with a diluting solvent, from the viewpoint of improving the coating properties by adjusting the viscosity.

Examples of the dilution solvent include aromatic hydrocarbons such as toluene, fatty acid esters such as ethyl acetate, ketones such as methyl ethyl ketone, organic solvents such as aliphatic hydrocarbons such as hexane and heptane, and the like. These dilution solvents may be used individually by 1 type, and may use 2 or more types together.

The solid content concentration of the coating agent containing the composition for forming a protective film is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. On the other hand, the solid content concentration of the coating agent containing the composition for the first release agent layer and the composition for the second release agent layer is preferably 0.3 to 10% by mass, more preferably 0.5 to 5% by mass, and still more preferably 0.5 to 3 mass %.

In this embodiment, after coating the coating agent containing the composition for a 1st release agent layer on one surface of a base material by a well-known method, the 1st release agent layer is formed by drying and hardening this coating film. Thus, a first release film was obtained. The second release film can also be produced in the same manner.

Then, when forming a release agent layer on both main surfaces of a base material, it can coat and form the coating agent of the composition for release agent layers on the other surface of a base material. Alternatively, it may be formed by winding the first release film formed by applying the coating agent of the release agent layer composition into a roll, and storing it at 30° C. for a period of 7 days, for example, to use The above-mentioned transfer phenomenon causes the components of the release agent layer composition to transfer to the other surface.

In this embodiment, the coating agent containing the composition for forming a protective film is applied on the first release agent layer of the first release film or the second release agent layer of the second release film by a known method, Then, heating and drying are performed to form a coating film. Next, the 2nd release agent layer of the 2nd release film, or the 1st release agent layer of the 1st release film is bonded together on this coating film, and the sheet (long sheet) for protective film formation is manufactured. In this embodiment, it is preferable to apply the coating agent containing the composition for protective film-forming films to the first part of the first release film from the viewpoint of making the peeling force F1 within the above-mentioned range and from the viewpoint of making F1>F2 on the release agent layer, not the second release agent layer.

As a coating method of the coating agent containing each composition, for example, a spin coating method, a spray coating method, a bar coating method, a blade coating method, a roll coating method, a roll blade coating method, and a blade coating method can be exemplified , Die coating method, Gravure coating method.

(3. Manufacturing method of the device) As an example of a manufacturing method using an apparatus using the sheet roll for forming a protective film produced by the method of the present embodiment, a process for producing a protective film-attached wafer obtained by processing a wafer to which the protective film forming film is attached is produced. The wafer method will be described.

First, as shown in FIG. 4 , the long sheet 1 is unwound from the sheet roll 100 for forming a protective film, and the dicing blade 50 is used to form on the long sheet penetrating the second peeling film 30 and the protective film forming film 10 , reaching to The cutout 40 of a part of the first release film 20 . A circular protective film-forming film can be obtained by removing the second release film and the unnecessary protective-film-forming film from the elongated sheet on which the slits 40 are formed.

Next, as shown in FIG. 5A , the circular protective film forming film 11 is attached to the back surface 60 b of the wafer 60 as a workpiece, and as shown in FIG. 5B , the first release film 20 is peeled off from the laminate and the protective film The forming film 11 is turned into a protective film to form a protective film 15 . Next, the wafer with a protective film is singulated to obtain a wafer with a protective film. In addition, the protective film can be formed after the wafers are singulated.

Since the formation of curl marks on the protective film forming film can be suppressed, the marks can also be suppressed on the surface of the protective film. Therefore, the wafer with a protective film in which the appearance defect of a protective film is suppressed can be obtained.

(4. Modifications) FIG. 3 shows a configuration in which the first release agent layer 23 is formed on the surface 20 a not in contact with the protective film forming film 10 in the first release film 20 , and the second release film 30 is formed on the surface 20 a not in contact with the protective film forming film 10 . The second release agent layer is not formed on the surface 30b in contact with the protective film forming film 10, but the present embodiment is not limited to this configuration.

For example, in the first release film, a first release agent layer may be formed on the surface that is not in contact with the protective film forming film, and in the second release film, a film not formed with the protective film may be formed. A second release agent layer is formed on the contact surface. In addition, in the first release film, the first release agent layer may not be formed on the surface that is not in contact with the protective film forming film, and the second release film may have a configuration in which the film is not formed with the protective film. A second release agent layer is formed on the contact surface.

In addition, in FIG. 4, although the incision for forming the protective film forming film to be attached to the workpiece|work is circular, as long as it is a closed shape, other shapes may be sufficient. As other shapes, for example, a polygon such as a triangle, an ellipse, or the like can be exemplified. Furthermore, it is preferable that the closed shape corresponds to the shape of the workpiece.

The embodiments of the present invention have been described above, but the present invention is not limited to the above-described embodiments at all, and can be changed in various ways within the scope of the present invention. [Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

(Production of the first release film) First, in order to prepare the composition for 1st release agent layers, the following components were prepared. (α) Silicon oxide mold release agent (α-1) Silicone-based mold release agent (manufactured by Dow Corning Toray Co., Ltd., BY24- 561, solid content 30% by mass) (α-2) Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-62-1387, weight average molecular weight: 2000) (β) Silicone resin MQ resin with vinyl group (manufactured by Dow Corning Toray Co., Ltd., SD-7292, solid content 71% by mass) (γ) Catalyst Platinum (Pt) catalyst (manufactured by Dow Corning Toray Co., Ltd., SRX-212, solid content 100% by mass)

Next, 67.5 parts by mass (solid content ratio) of (α-1), 2.5 parts by mass (solid content ratio) of (α-2), 30 parts by mass (solid content ratio) of (β), and 6.7 parts by mass were blended (solid content ratio) (γ) and mixed, using a mixed solvent of toluene and methyl ethyl ketone (toluene/methyl ethyl ketone = 1/1 (mass ratio)) with a solid content concentration of 2 mass % Diluted in a manner to prepare a coating agent containing the composition for the first release agent layer.

The coating agent containing the prepared composition for forming a first release agent layer was coated on a PET film (manufactured by Mitsubishi Chemical Corporation, trade name: DIAFOIL) as a base material so that the film thickness after heating and drying was 0.15 μm. (registered trademark) T-100, thickness: 50 μm) on both main surfaces, a first release agent layer was formed on both main surfaces of a PET film to prepare a first release film.

(Production of the second release film) As a 2nd peeling film, the film ("SP-PET381031" manufactured by Lintec Corporation, thickness 38 micrometers) whose one surface of a PET film was peeled was used.

(Production of protective film forming film) The following components were mixed at the blending ratio (in terms of solid content) shown in Table 1, and diluted with methyl ethyl ketone so that the solid content concentration might be 50% by mass to prepare a coating containing the composition for forming a protective film. Cloth. (A) Polymer component (A-1) (meth)acrylate obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate Copolymer (weight average molecular weight: 800,000, glass transition temperature: -28°C) (A-2) (meth)acrylate obtained by copolymerizing 27 parts by mass of n-butyl acrylate, 38 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate Copolymer (weight average molecular weight: 500,000, glass transition temperature: -9°C) (B) Curable component (thermosetting component) (B-1) Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828, epoxy equivalent 184-194 g/eq) (B-2) Acrylate rubber microparticle-dispersed bisphenol A type liquid epoxy resin (manufactured by NIPPON SHOKUBAI CO., LTD., BPA328, epoxy equivalent 230 g/eq, acrylate rubber content 20 phr) (B-3) Dicyclopentadiene type epoxy resin (manufactured by DIC CORPORATION, EPICLON HP-7200HH, softening point 88~98°C, epoxy equivalent 255~260g/eq) (C) Curing agent: Dicyandiamide (manufactured by Mitsubishi Chemical Corporation, DICY7) (D) Curing accelerator: 2-phenyl-4,5-dimethylolimidazole (manufactured by SHIKOKU CHEMICALS CORPORATION, CUREZOL 2PHZ) (E) Filling material: Epoxy modified spherical silica filler (manufactured by Admatechs, SC2050MA, average particle size 0.5 μm) (F) Silane coupling agent: γ-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403, methoxyl equivalent 12.7 mmol/g, molecular weight 236.3) (G) Colorant: carbon black (manufactured by Mitsubishi Chemical Corporation, MA600B, average particle size 28 nm)

The coating agent containing the prepared composition for forming a protective film was applied on the surface of the prepared first release film on which the first release agent layer was formed, and dried at 100° C. for 2 minutes to form a protective film having a thickness of 20 μm form a film. Next, the surface of the prepared second release film on which the second release agent layer is formed is attached to the protective film-forming film, whereby the first release film is formed on one main surface of the protective film-forming film, and the other is formed on the other main surface. A sheet for forming a protective film (a structure of a first peeling film/protective film forming film/second peeling film) having a second peeling film formed on one main surface. The attachment conditions were a temperature of 60° C., a pressure of 0.4 MPa, and a speed of 1 m/min.

(production of rolls) While cutting the obtained sheet for forming a protective film into a width of 320 mm using a biaxial winding slitter (manufactured by TOIZAKI BUSSAN CO., LTD.), the cutout was protected by a core fixing tape with a width of 5 mm and a thickness of 40 μm. The film-forming sheet is wound in a roll on a hollow plastic core (core) having the same width (320 mm) as the protective film-forming sheet is cut out and having a diameter of 3 inches . The winding condition is a condition in which the ammeter of the magnetic powder brake for controlling the tension during winding shows 0.25 A. The length of the sheet for protective film formation wound up was 50 m. The cutting speed is 5m/min.

By storing the wound sheet for protective film formation (Examples 1 to 3 and Comparative Examples 1 to 2) under the storage conditions (patterns 1 to 4) shown below, a sheet roll for protective film formation was obtained.

In Mode 1, after being left at 23° C. for 3 days after winding, it was left at 5±4° C. for 40 days, and again at 23° C. for 17 days (Example 1 and Comparative Example 1). In mode 2, after being left at 23°C for 3 days after winding, it was left at 5±4°C for 50 days, and again at 23°C for 7 days (Example 2). In mode 3, after being left at 23°C for 3 days after winding, it was left at 5±4°C for 30 days, and again at 23°C for 27 days (Example 3). In Mode 4, it was left to stand at 23° C. for 60 days after winding (Comparative Example 4).

Next, the following measurement and evaluation were performed.

(Loss tangent tanδ ₁₀ of protective film forming film at 10° C.) The first release film and the second release film were peeled from the produced protective film forming sheet, and a plurality of protective film forming films were laminated to have a thickness of 200 μm± The protective film of 20 micrometers forms the laminated body of a film. This laminated body was cut|disconnected so that the width|variety might be 4 mm, and the sample for measurement was obtained.

Using a viscoelasticity measuring device (“RHEOVIBRON DDV-01FP” manufactured by ORIENTEC Co., Ltd.), the above-mentioned measurement samples were measured under the measurement conditions of a frequency of 11 Hz, a distance between chucks of 15 mm, and a heating rate of 3°C/min. The tanδ of the measurement sample at -20°C to 50°C was measured in the tensile mode, and the loss tangent tanδ ₁₀ at 10°C was calculated from these values. Table 1 shows the measurement results of the samples of Examples 1 to 3 and Comparative Examples 1 and 2.

(Evaluation of presence or absence of peeling treatment of peeling film) From the obtained sheet roll, the sheet for forming a protective film was unwound, and at a position of 1 m from the starting part where the sheet for forming a protective film was fixed to the plastic core by the core fixing tape, three places of 50 mm × 50 mm were cut in the width direction. 50mm sheet for forming a protective film.

The 1st peeling film and the 2nd peeling film were peeled off from the sheet for protective film formation cut out, and the XPS measurement was performed on the surface which is not bonded to the protective film forming film in the first peeling film under the following conditions. Similarly, XPS measurement was performed on the surface not bonded to the protective film-forming film in the second release film under the following conditions. The XPS measurement was performed once for each of three first release films and three second release films obtained by cutting out the sheet for protective film formation. XPS unit: QuanteraSXM by ULVAC-PHI, INCORPORATED. X-ray: AlKα (1486.6eV) Take-out angle: 45° Determination elements: silicon (Si), carbon (C), oxygen atom (O)

Based on the obtained measurement results, the silicon atomic ratio shown below was calculated from the amount of each measurement element (XPS count) for the first release film and the second release film, and the average value was calculated. Silicon atomic ratio (atomic %) = [(Si element amount)/[(C element amount) + (O element amount) + (Si element amount)]]×100

Based on the obtained average value, evaluation was performed using the following judgment criteria. The cases of Judgment A and Judgment B were judged as having undergone the peeling process. Table 1 shows the measurement results of the samples of Examples 1 to 3 and Comparative Examples 1 and 2. Judgment A: The average value of at least one of the first release film and the second release film is 1.0 atomic % or more Judgment B: Judgment A is not satisfied, and the average value of at least one of the first release film and the second release film is 0.1 atomic % or more and less than 1.0 atomic % Judgment C: The average value of both the first release film and the second release film is less than 0.1 atomic %

The 1st release film before coating the coating agent containing the composition for protective film-forming films was prepared, and cut out 3 places in the width direction from the 1st release film in the size of 50 mm x 50 mm. Using the said XPS apparatus, the presence or absence of a peeling process was evaluated with respect to the surface to which the coating agent containing the composition for protective film-forming films is to be applied among the two main surfaces of the first release film under the same conditions as described above. As a result, in the sample of the first release film, it was confirmed that the average value of the silicon atomic ratio was 1.0 atomic % or more in three places.

The 2nd peeling film before sticking to the protective film formation film was prepared, and it cut out 3 places in the width direction from the 2nd peeling film in the size of 50 mm x 50 mm. Using the said XPS apparatus, the presence or absence of a peeling process was evaluated with respect to the surface to be attached to the protective film forming film among the two main surfaces of the 2nd peeling film under the same conditions as the above. As a result, in the sample of the second release film, it was confirmed that the average value of the silicon atomic ratio was 1.0 atomic % or more in three places.

(Evaluation of water contact angle of peeling film) From the obtained sheet roll, the sheet for forming a protective film was unwound, and at a position of 1 m from the starting part where the sheet for forming a protective film was fixed to the plastic core by the core fixing tape, three places of 50 mm × 50 mm were cut in the width direction. 50mm sheet for forming a protective film.

The 1st peeling film and the 2nd peeling film were peeled off from the sheet for protective film formation cut out, and the contact angle of water was measured on the surface which is not bonded to the protective film forming film among the first peeling films under the following conditions. In the same manner, the contact angle of water was measured on the surface not bonded to the protective film-forming film in the second release film under the following conditions. The measurement of the contact angle of water was performed 5 times each about 3 sheets of 1st peeling films and 3 sheets of 2nd peeling films obtained by cutting out the sheet for protective film formation. Contact angle measuring device: Kyowa Interface Science, Inc., fully automatic contact angle meter DM-701 Dropping volume: 2μL Environment: temperature 23℃, humidity 50%

About the 1st peeling film and the 2nd peeling film, the average value of the obtained measurement result was computed, respectively. Based on the obtained average value, evaluation was performed using the following judgment criteria. In the case of determination A, it was determined that the peeling process was performed. Table 1 shows the measurement results of the samples of Examples 1 to 3 and Comparative Examples 1 and 2. Judgment A: The average value of at least one of the first release film and the second release film is 78 or more Judgment C: The average value of both the first release film and the second release film is 77 or less

(Peeling force F1 for peeling the first peeling film from the protective film forming film) The second release film was peeled off from the obtained sheet for forming a protective film. By thermal lamination (70° C., 1 m/min), the well-adhesive PET (PET25A-4100, manufactured by TOYOBO Co., Ltd.) with a thickness of 25 μm was attached to the protective film-forming film exposed by peeling. surface to produce laminate samples. The laminate sample was cut into a width of 100 mm to prepare a sample for measurement. The back surface of the 1st release film of the sample for a measurement was fixed to the hard support plate with the double-sided tape.

Using a universal tensile tester (manufactured by Shimadzu Corporation, product name "AUTOGRAPH (registered trademark) AG-IS"), the protective film was formed into a film/ The composite (integrated) body of the well-adhered PET was peeled off from the first release film, and the load at that time was measured. Among the measured loads, the average value of the loads between 80 mm except the load of the first 10 mm and the load of the last 10 mm of the measurement distance was taken as the peeling force F1.

(Peeling force F2 for peeling the second peeling film from the protective film forming film) The obtained sheet for forming a protective film was cut into a width of 100 mm to prepare a sample for measurement. The back surface of the 1st release film of the sample for a measurement was fixed to the hard support plate with the double-sided tape.

Using a universal tensile tester (manufactured by Shimadzu Corporation, product name "AUTOGRAPH (registered trademark) AG-IS"), the second release film was subjected to a measurement distance of 100 mm, a peeling angle of 180°, and a peeling speed of 1 m/min. The sample for measurement was peeled off, and the load at that time was measured. Among the measured loads, the average value of the loads between 80 mm except the load of the first 10 mm and the load of the last 10 mm of the measurement distance was taken as the peeling force F2.

The obtained peel forces F1 and F2 were compared, and it was confirmed that F1 was larger than F2 in all the samples.

(evaluation of curl marks) The long sheet was unwound at a speed of 3 m/min from the outermost layer from the roll for forming a protective film after storage for 60 days, and the "length from the core" at which a roll mark outside the allowable range began to appear was measured. Five judges simultaneously checked whether the curl marks were outside the allowable range with the naked eye, and when three judges judged that the curl marks were outside the allowable range, they were judged as curl marks outside the allowable range. Table 1 shows the evaluation results of the samples of Examples 1 to 3 and Comparative Examples 1 and 2. Judgment A: more than 0 meters, less than 4 meters Judgment B: more than 4 meters, less than 6 meters Judgment C: more than 6 meters, less than 8 meters Judgment D: more than 8 meters, less than 10 meters Judgment E: 10 meters or more

[Table 1]

According to Table 1, when the loss tangent (tanδ ₁₀ ) of the protective film forming film at 10° C. is 1.2 or less and the storage conditions of the roll for protective film forming after winding satisfies the above conditions, the protective film forming sheet The formation of roll marks on the protective film forming film in the roll is suppressed.

1: Sheet for forming protective film 10,11: Protective film forming film 10a, 10b, 20b, 30a: main surface 15: protective film 20: First release film 20a, 30b: face 21: Substrate 22, 23: First release agent layer 30: Second release film 31: Substrate 32: Second release agent layer 40: Cut 50: Cutting Blade 60: Wafer 60b: Back 70: Core 80: Fixing tools 100: Sheet roll for forming protective film IB: Part

1A is a schematic perspective view of an example of the sheet roll for forming a protective film of the present embodiment. FIG. 1B is an enlarged schematic cross-sectional view of portion IB of FIG. 1A . 2 is a schematic cross-sectional view of an example of the protective film-forming sheet of the present embodiment. 3 is a schematic cross-sectional view showing that a first release film and a second release film have a first release agent layer and a second release agent layer. 4 : is a perspective schematic diagram of the elongate sheet|seat in which the slit was formed by unwinding from the sheet roll for protective film formation of this embodiment. 5A is a schematic cross-sectional view showing that a laminate of a protective film forming film and a first release film is attached to a workpiece. 5B is a schematic cross-sectional view showing that the protective film-forming film attached to the workpiece is formed into a protective film.

1: Sheet for forming protective film

100: Sheet roll for forming protective film

IB: Part

Claims (5)

A method for producing a sheet roll for forming a protective film, comprising: winding a protective film forming film, a first release film provided on one surface of the protective film forming film, and a first release film provided on the protective film forming film The sheet roll formed by the long piece of the second peeling film on the other side of the sheet, the step of storing at a storage temperature of 10°C or less for 25 days or more within 60 days after the formation of the sheet roll, will be removed from the When the peeling force for peeling off the first release film from the protective film forming film is F1, and the peeling force for peeling the second peeling film from the protective film forming film is F2, F1>F2 is satisfied. In relation, when the loss tangent of the protective film forming film at 10° C. is tanδ ₁₀ , tanδ ₁₀ is 1.2 or less. The manufacturing method of the sheet roll for protective film formation according to claim 1, wherein the step of storing at a storage temperature of 10° C. or lower is started within 10 days after the sheet roll is formed. The manufacturing method of the sheet roll for protective film formation as described in Claim 1 or 2 whose said storage temperature is -10 degreeC or more. The method for producing a sheet roll for forming a protective film according to any one of claims 1 to 3, wherein the first release film and/or the second release film is not formed with the protective film The side where the films meet is peeled off. The manufacturing method of the sheet roll for protective film formation in any one of Claims 1-4 whose tan delta ₁₀ is 0.04 or more.

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