CN114075419A - Protective film forming sheet and method for processing protective film forming sheet - Google Patents
Protective film forming sheet and method for processing protective film forming sheet Download PDFInfo
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- CN114075419A CN114075419A CN202110737279.1A CN202110737279A CN114075419A CN 114075419 A CN114075419 A CN 114075419A CN 202110737279 A CN202110737279 A CN 202110737279A CN 114075419 A CN114075419 A CN 114075419A
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- Prior art keywords
- protective film
- film
- forming
- release
- film forming
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/04—Punching, slitting or perforating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/04—Punching, slitting or perforating
- B32B2038/042—Punching
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
Landscapes
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- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Dicing (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a sheet for forming a protective film, which can inhibit the formation of floating between a protective film forming film and a support film even when the protective film forming film is cut by using a cutting blade, and a method for processing the sheet for forming the protective film. The protective film-forming sheet comprises a protective film-forming film and a first release film arranged on one main surface of the protective film-forming film in a peelable manner, wherein the probe tack value of the protective film-forming film at 23 ℃ is less than 6200mN, the surface elastic modulus of the surface of the first release film in contact with the protective film-forming film at 23 ℃ is 17MPa or less, and the product of the probe tack value and the surface elastic modulus is 66000 or less.
Description
Technical Field
The present invention relates to a protective film forming sheet and a method for processing the protective film forming sheet. In particular, the present invention relates to a protective film forming sheet which is less likely to cause floating, which may become a peeling starting point or mark on the protective film, and a method for processing the protective film forming sheet.
Background
In recent years, semiconductor devices are being manufactured by a mounting method called flip chip bonding. In this mounting method, when a semiconductor chip having a circuit surface on which convex electrodes such as bumps (bumps) are formed is mounted, the circuit surface side of the semiconductor chip is turned over (face down) and bonded to the chip mounting portion. Therefore, the semiconductor device has a structure in which the back surface side of the semiconductor chip on which no circuit is formed is exposed.
Therefore, in order to protect the semiconductor chip 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 chip. Such a protective film is formed by curing or in a non-cured state after a protective film forming film is attached to the back surface of a semiconductor wafer, for example.
The protective film forming film and a support film supporting the protective film forming film together constitute a long protective film forming sheet. Before forming a film using the protective film, the long strip-shaped sheet is generally wound into a sheet roll. When the protective film is used to form a film, a long protective film-forming sheet unwound from a roll is cut into substantially the same shape as the semiconductor wafer to which the sheet is attached, and then the cut sheet is attached to the semiconductor wafer.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2017/145735
Disclosure of Invention
Technical problem to be solved by the invention
When the protective film is used to form a film, the protective film forming film having a predetermined shape is cut out from the protective film forming sheet as described above. The cutting out of the protective film forming film generally uses a punching blade. In the cutting process using the punching blade, the punching blade enters the protective film forming film to cut the protective film forming film, and stops when reaching the middle of the supporting film. Next, by pulling out the punching blade, the protective film forming film on the inner side of the punching blade is completely separated from the protective film forming film on the outer side of the punching blade, resulting in a protective film forming film having a closed shape.
However, in the cutting process, the protective film forming film comes into contact with the punching blade, and therefore the protective film forming film easily adheres to the punching blade. Therefore, there are the following problems: when the punching blade is pulled out, the protective film forming film near the punching blade is stretched and deformed in a state of being attached to the punching blade accompanying the pulling-out of the punching blade, and is peeled from the support film.
The portion of the protective film forming film peeled off from the support film becomes floating. If such a floating occurs, in the step of removing the outer protective film forming film of the punching blade to obtain the inner protective film forming film of the punching blade, the floating becomes a starting point of peeling when the outer protective film forming film is removed, and the inner protective film forming film to be left is also peeled off and removed by accident.
In addition, in the protective film forming film, a mark due to peeling is likely to occur on the surface of a portion peeled from the support film. The surface of the protective film forming film, which is connected with the support film, is exposed to the outside after the protective film forming film is attached to the back surface of the wafer. Therefore, the portion peeled from the support film to form the trace is also exposed to the outside. As a result, the mark causes poor appearance of the protective film.
In addition, since the above-mentioned mark is formed when the protective film forming film is peeled off from the support film, the mark tends not to disappear and remain even if the protective film forming film is bonded to the support film again after peeling.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a protective film forming sheet in which the formation of floating between a protective film forming film and a support film is suppressed even when the protective film forming film is cut out using a dicing blade, and a method of processing the protective film forming sheet.
Means for solving the problems
The scheme of the invention is as follows.
[1] A protective film-forming sheet comprising a protective film-forming film and a first release film arranged so as to be peelable from one main surface of the protective film-forming film,
the probe tack value of the protective film forming film at 23 ℃ is smaller than 6200mN,
the surface elastic modulus of the surface of the first release film in contact with the protective film forming film at 23 ℃ is 17MPa or less,
the product of the viscosity value of the probe and the surface elastic modulus is 66000 or less
[2] The protective film-forming sheet according to [1], wherein the first release film comprises a base material and a first release agent layer formed on one main surface of the base material, and the first release agent layer is in contact with the protective film-forming film.
[3] The protective film-forming sheet according to [1] or [2], which comprises a second release film peelably disposed on the other main surface of the protective film-forming film,
when the peeling force for peeling the first release film from the protective film forming film is F1 and the peeling force for peeling the second release film from the protective film forming film is F2, F1 and F2 satisfy the relationship of F1 > F2.
[4] The protective film-forming sheet according to any one of [1] to [3], wherein the first release agent layer has a thickness in a range of 30nm to 200 nm.
[5] The protective film forming sheet according to any one of [1] to [4], wherein the protective film forming sheet has a cutout formed so that a part of the protective film forming sheet has a predetermined closed shape when the protective film forming sheet is viewed in plan,
the cut penetrates the protective film forming film in the thickness direction of the protective film forming sheet and reaches a part of the first release film.
[6] The protective film forming sheet according to [5], wherein a maximum value of a distance between the end face and a portion where floating formed between the protective film forming film and the first release film is observed is less than 4mm in a direction from the end face of the protective film forming film having the closed shape toward a center of the protective film forming film.
[7] A method for processing a protective film-forming sheet, comprising a step of forming a notch so that a part of the protective film-forming sheet described in any one of [1] to [4] has a predetermined closed shape,
the cut penetrates the protective film forming film in the thickness direction of the protective film forming sheet and reaches a part of the first release film.
Effects of the invention
According to the present invention, it is possible to provide a protective film forming sheet in which formation of floating between a protective film forming film and a support film is suppressed even in the case where the protective film forming film is cut out using a dicing blade, and a method of processing the protective film forming sheet.
Drawings
Fig. 1A is a schematic cross-sectional view of one example of the protective film-forming sheet of the present embodiment.
Fig. 1B is a schematic cross-sectional view of another example of the protective film-forming sheet of the present embodiment.
Fig. 2A is a perspective view for explaining a step of forming a slit in the long protective film forming sheet in the present embodiment.
Fig. 2B is a schematic cross-sectional view of a long protective film-forming sheet having a slit formed therein.
Fig. 2C is a schematic cross-sectional view of the protective film forming sheet after removing the protective film forming film and the second release film except the circular protective film forming film from the long protective film forming sheet in which the slits are formed.
Fig. 3A is a schematic cross-sectional view for explaining a case where a float is formed when the cutting blade is pulled out.
Fig. 3B is a schematic cross-sectional view showing a laminate in which a floating protective film forming film and a first release film are formed.
Fig. 3C is a schematic plan view showing a laminate of the floating protective film forming film and the first release film formed thereon, as viewed from the direction of the arrow shown in fig. 3B.
Fig. 3D is a schematic cross-sectional view for explaining a case where the formation of floating at the time of pulling out the dicing blade of the protective film forming sheet of the present embodiment is suppressed.
Fig. 4 is a schematic cross-sectional view showing that the first and second release films have the first and second release agent layers.
Fig. 5 is a perspective view of a long protective film forming sheet in which a slit is formed by unwinding from a roll of the protective film forming sheet of the present embodiment.
Fig. 6A is a schematic sectional view showing the protective film-forming sheet shown in fig. 2C attached to a workpiece.
Fig. 6B is a schematic cross-sectional view showing that the protective film attached to the workpiece is formed into a protective film.
Description of the reference numerals
1: a protective film-forming sheet; 10: forming a film by the protective film; 11: forming a circular protective film; 12: a protection film forming film other than the circular protection film forming film; 20: a first release film; 21: a substrate; 22: a first release agent layer; 30: a second release film; 31: a substrate; 32: a second release agent layer; 40: cutting; 50: and (4) cutting the blade.
Detailed Description
Hereinafter, the present invention will be described in detail based on specific embodiments with reference to the accompanying drawings.
First, main terms used in the present specification will be described.
The workpiece is a plate-shaped body which is attached with a protective film to form a film and is to be processed. Examples of the workpiece include a wafer and a panel. Specifically, a semiconductor wafer and a semiconductor panel are exemplified. Examples of the workpiece to be processed include a wafer (single wafer) and a chip obtained by singulating the wafer. Specifically, a semiconductor wafer is singulated to obtain semiconductor chips. At this time, the protective film is formed on the back surface side of the wafer.
The "front surface" of the workpiece refers to a surface on which a circuit, a convex electrode such as a bump, or the like is formed, and the "back surface" refers to a surface on which no circuit or the like is formed.
In the present specification, for example, "(meth) acrylate" is used as a term indicating both "acrylate" and "methacrylate", and other similar terms are also used.
In the present specification, the weight ratio of the components constituting each composition is expressed as a solid content ratio.
(1. sheet for Forming protective film)
As shown in fig. 1A, the protective film forming sheet 1 of the present embodiment has a structure in which a first release film 20 for supporting the protective film forming film 10 is disposed on one main surface 10a of the protective film forming film 10, and a second release film 30 is disposed on the other main surface 10 b.
The protective film-forming sheet 1 of the present embodiment is not limited to the configuration shown in fig. 1A. For example, the protective film-forming sheet may be configured without any one of the first release film and the second release film. Fig. 1B shows a protective film forming sheet 1 having a structure in which a first release film 20 is disposed on one main surface 10a of a protective film forming film 10.
Although the following description will be made using a protective film forming sheet having the structure shown in fig. 1A, the following description is naturally applicable to the structure shown in fig. 1B.
In the present embodiment, the protective film-forming sheet is used for attaching the protective film-forming film to the workpiece. The protective film forming film is attached to a workpiece and then formed into a protective film, thereby forming a protective film for protecting the workpiece or a workpiece to be processed.
In the present embodiment, in order to attach the protective film forming film to the workpiece, the protective film forming film having a predetermined closed shape is cut out from the protective film forming sheet 1 shown in fig. 1A. Specifically, a circular cut is formed from the second release film 30 side along the predetermined cut position 40a on the protective film forming sheet 1 shown in fig. 2A by a dicing blade 50, thereby forming a circular protective film forming film. As shown in fig. 2B, the slit 40 penetrates the second release film 30 and the protective film forming film 10, reaches a part of the first release film 20, and is divided into a circular protective film forming film 11 and the other protective film forming films 12.
Next, as shown in fig. 2C, the second release film 30 and the protective film forming films 12 other than the circular protective film forming film 11 are removed from the protective film forming sheet 1, thereby obtaining the circular protective film forming film 11 and the long-sized first release film 20. The protective film forming film of the laminate is attached to the back surface of the workpiece, the first release film is peeled off, and the protective film forming film is formed into a protective film.
As shown in fig. 2A, the protective film forming sheet 1 is preferably a long sheet in which a plurality of protective film forming films 11 to be attached to a workpiece can be formed. The protective film forming sheet 1 is also preferably a sheet roll formed by winding the long sheet. The protective film forming sheet 1 may be a single sheet obtained by cutting a long protective film forming sheet to form a single protective film forming film 11 to be attached to a workpiece.
When the cut is formed, after the protective film forming film is brought into contact with the cutting blade for a short time, the cutting blade is separated from the protective film forming film. At this time, since tackiness is generated on the protective film forming film, the protective film forming film easily adheres to the dicing blade. Therefore, as shown in fig. 3A, when the dicing blade 50 is pulled out after the protective film forming film 10 is cut, the protective film forming film 10 near the dicing blade 50 tends to be stretched and deformed in a state of adhering to the dicing blade 50 along with the pulling out of the dicing blade 50. Then, finally, the protective film forming film 10 is peeled off from the first peeling film 20, and the float a is formed between the protective film forming film 10 and the first peeling film 20. Fig. 3B shows a laminate of the protective film forming film 11 on which the float a is formed and the first release film 20. Fig. 3C shows a float a formed in the laminate of the protective film forming film 11 and the first release film 20 when viewed from the direction of the arrow shown in fig. 3B.
This floating becomes a starting point from which the protective film forming film is peeled off from the first release film. Therefore, when the lift-off is formed, and the second release film 30 and the protective film forming film 12 other than the circular protective film forming film 11 are removed from the long first release film 20 after the protective film forming film is cut out, the following cases may occur: although not originally a peeling process, the circular protective film forming film 11 is also accidentally peeled from the first peeling film 20, and a part or all of the protective film forming film 11 is removed together with the second peeling film 30. If the protective film forming film 11 is peeled off, the protective film forming sheet 1, which is not the protective film forming film 11 to be stuck to the workpiece, is conveyed to the next step, which causes a problem.
Further, in the protective film forming film, marks are likely to occur in the floating of the peeling from the first release film due to the pulling out of the dicing blade. The surface of the protective film forming film which is in contact with the first release film is attached to the back surface of the wafer, and the first release film is peeled off to expose the surface to the outside. Therefore, the float is also exposed to the outside. That is, since the trace is exposed to the outside, the protective film including the trace is determined to have a poor appearance.
Further, since the above-mentioned mark is formed when the protective film forming film is peeled off from the first release film, even if the protective film forming film is bonded to the first release film again after peeling, the mark tends not to disappear and to remain after the protective film is formed.
In contrast, since the protective film-forming sheet of the present embodiment has the characteristics described below, the protective film-forming film is less likely to adhere to the dicing blade when the dicing blade is pulled out, and the formation of floating can be suppressed. As a result, the protective film forming film 11 can be prevented from being unintentionally peeled off from the first release film 20 and the appearance of the protective film can be prevented from being deteriorated.
As shown in fig. 3C, in the laminate of the protective film forming film 11 and the first release film 20 according to the present embodiment, when the maximum value D of the distance from the end face to the portion where the floating a is observed in the direction from the end face of the protective film forming film 11 toward the center O of the protective film forming film 11 is less than 4mm, it is judged that the floating formation can be suppressed. Hereinafter, the constituent elements of the protective film forming sheet 1 will be described in detail.
(2. protective film forming film)
As described above, the protective film forming film is attached to the workpiece and then formed into a protective film, thereby forming a protective film for protecting the workpiece or the workpiece to be processed.
The "protective film formation" refers to a state in which a protective film is formed to have sufficient characteristics for protecting a workpiece or a processed object of the workpiece. Specifically, when the protective film forming film is curable, "forming a protective film" means forming an uncured protective film forming film into a cured product. In other words, the protective 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 the work is laminated on the curable protective film forming film, the protective film can be firmly adhered to the work by curing the protective film forming film, and a protective film having durability 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 is formed into a protective film at the time when the protective film forming film is attached to a 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, it is not necessary to cure the protective film forming film, and therefore the protective film forming film is easy to use.
In the present embodiment, the protective film forming film is preferably curable. Therefore, the protective film is preferably a cured product. Examples of the cured product include a thermal cured product and an energy ray cured product. In the present embodiment, the protective film is more preferably a thermoset.
Further, the protective film forming film preferably has adhesiveness at normal temperature (23 ℃) or exhibits adhesiveness by heating. Thus, the protective film forming film and the workpiece can be bonded together when the workpiece is stacked thereon. Therefore, positioning can be performed with certainty 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 as 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 protective film forming film of one layer can be obtained with high precision in thickness and is therefore easy to produce. Further, if the protective film forming film is composed of a plurality of layers, it is necessary to consider the adhesiveness between the layers and the stretchability of each layer, and there is a risk that peeling from the adherend occurs due to this. When the protective film is formed as one layer, the above 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, and 30 μm or less. When the upper limit value of the thickness of the protective film forming film is set to the above value, the protective film forming film in the vicinity of the dicing blade can be prevented from being stretched and deformed in a state of adhering to the dicing blade as the dicing blade is pulled out.
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 value of the thickness of the protective film forming film to the above value, as the protective film, the performance of protecting the workpiece is easily obtained.
The thickness of the protective film forming film is the thickness of the entire protective film forming film. For example, the thickness of the protective film forming film composed of a plurality of layers means the total thickness of all the layers constituting the protective film forming film.
(2.1 Probe tack value at 23 ℃ for protective film-forming film)
In the present embodiment, the probe tack value of the protective film forming film at 23 ℃ is less than 6200mN, which is an index of the adhesive force exhibited in a short time after contact with the adherend. As shown in fig. 3D, by making the probe tack value of the protective film-forming film at 23 ℃ within the above range, it is possible to suppress: the protective film forming film 10 is in contact with and strongly adheres to the dicing blade 50, and when the dicing blade 50 is pulled out, the protective film forming film 10 is stretched and deformed in a state of adhering to the dicing blade 50. As a result, it is possible to suppress: the protective film forming film 10 is excessively stretched (deformed), and peeled off from the first release film 20 to float.
The probe tack value of the protective film forming film at 23 ℃ is preferably 5900mN or less, 5400mN or less, 4900mN or less, 4400mN or less, and 4000mN or less. The lower limit of the probe viscosity of the protective film forming film at 23 ℃ is not particularly limited, but in the present embodiment, 50mN, 200mN, 500mN, and 1000mN are preferable. By setting the lower limit of the probe tack value at 23 ℃ to the above value, the applicable temperature range when attaching the protective film-forming film to the workpiece is wide.
The value of the probe tack of the protective film-forming film at 23 ℃ can be measured according to JIS Z0237: 1991 reference 5 and using a well-known probe tack testing apparatus. That is, the value of the probe tack of the protective film forming film at 23 ℃ can be measured by the same method as that described in JIS Z0237: 1991 reference 5, but can also be measured under conditions different from the test conditions described in JIS Z0237: 1991 reference 5. The specific measurement method will be described in detail in the examples below.
(2.2 composition for Forming 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 physical properties. In the present embodiment, the composition constituting the protective film-forming film (the composition for forming a protective film) is preferably a resin composition containing at least the polymer component (a), the curable component (B), and the filler (E). The polymer component can be considered as a component formed by a polymerization reaction of a polymerizable compound. The curable component is a component capable of undergoing a curing (polymerization) reaction. The polymerization reaction in the present invention also includes a polycondensation reaction.
Further, components contained in the polymer component may be a curable component. In the present embodiment, when the composition for forming a protective film contains such a component that belongs to both the polymer component and the curable component, it is regarded that the composition for forming a protective film contains both the polymer component and the curable component.
(2.2.1 Polymer component)
The polymer component (a) imparts film formability (film formability) to the protective film-forming film and provides appropriate viscosity, thereby reliably and uniformly adhering the protective film-forming film to the workpiece. The weight average molecular weight of the polymer component is usually in the range of 5 to 200 ten thousand, preferably 10 to 150 ten thousand, and particularly preferably 20 to 100 ten thousand. As such a polymer component, for example, an acrylic resin, a urethane resin, a phenoxy resin, a silicone resin, a saturated polyester resin, or the like can be used, and an acrylic resin is particularly preferably used.
In addition, in the present specification, unless otherwise specified, "weight average molecular weight" means a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method. The measurement based on this method can be performed, for example, in the following manner: used in TOSOH CA high performance GPC device "HLC-8120 GPC" manufactured by ORPORATION is sequentially connected with a high performance chromatographic column "TSK guard column HXL-H”、“TSK Gel GMHXL”、“TSK Gel G2000 HXL"(all manufactured by TOSOH CORPORATION) at a column temperature: 40 ℃ and liquid inlet speed: under the condition of 1.0 mL/min, the detector was set as a differential refractometer.
Examples of the acrylic resin include (meth) acrylate copolymers composed of a (meth) acrylate monomer and a structural unit derived from a (meth) acrylic acid derivative. The (meth) acrylate monomer preferably includes an alkyl (meth) acrylate having an alkyl group with 1 to 18 carbon atoms, and specifically includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Examples of the (meth) acrylic acid derivative include (meth) acrylic acid, glycidyl (meth) acrylate, and hydroxyethyl (meth) acrylate.
In the present embodiment, glycidyl groups are preferably introduced into the acrylic resin using glycidyl methacrylate or the like. The acrylic resin having a glycidyl group introduced therein has improved compatibility with an epoxy resin as a thermosetting component described later, and tends to easily obtain a protective film-forming film having stable properties (including a probe tack value). In the present embodiment, it is preferable to introduce a hydroxyl group into an acrylic resin using hydroxyethyl acrylate or the like in order to control adhesiveness to a work or adhesive properties.
The glass transition temperature of the acrylic resin is preferably-70-40 ℃, 35-35 ℃, 20-30 ℃, 10-25 ℃ and 5-20 ℃. When the lower limit of the glass transition temperature of the acrylic resin is set to the above value, the adhesiveness of the protective film forming film is easily reduced. When the upper limit value of the glass transition temperature of the acrylic resin is set to the above value, the adhesion of the protective film forming film to the work is suitably improved, and the adhesion of the protective film to the work is suitably improved.
When the acrylic resin has m kinds of structural units (m is an integer of 2 or more), the glass transition temperature of the acrylic resin can be calculated as follows. That is, when m kinds of monomers from which the structural units in the acrylic resin are derived are sequentially assigned with numbers that do not overlap from 1 to m, and are named as "monomers m", the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox equation shown below.
[ mathematical formula 1]
Wherein 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 a homopolymer of monomer m; wk is the mass fraction of a structural unit m derived from a monomer m in the acrylic resin, wherein Wk satisfies the following formula.
[ mathematical formula 2]
Wherein m and Wk are the same as those described above.
As Tgk, the values described in the Polymer data manual (polymers データ and ハンドブック), the adhesion manual (adhesion ハンドブック), or Polymer Handbook, etc. can be used. For example, a homopolymer of methyl acrylate is Tgk deg.C, a homopolymer of n-butyl acrylate is Tgk deg.C-54 deg.C, a homopolymer of methyl methacrylate is Tgk deg.C-105 deg.C, a homopolymer of 2-hydroxyethyl acrylate is Tgk deg.C-15 deg.C, a homopolymer of glycidyl methacrylate is Tgk deg.C 41 deg.C, and a homopolymer of 2-ethylhexyl acrylate is Tgk deg.C-70 deg.C.
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 to 50 parts by mass, or 15 to 45 parts by mass, based on 100 parts by mass of the total weight of the composition for forming a protective film. When the content of the polymer component is in the above range, the viscosity of the protective film forming film can be easily controlled, and therefore the above-mentioned probe viscosity value can be easily controlled.
(2.2.2 thermosetting Components)
The curable component (B) forms a hard coating by curing the coating film-forming film. As the curable component, a thermosetting component, an energy ray curable component, or a mixture thereof can be used. When the protective film is cured by irradiation with energy rays, the protective film formation film contains a filler, a colorant, and the like described later, and therefore light transmittance is reduced. Therefore, for example, when the thickness of the protective film forming film is increased, the energy ray curing is likely to be insufficient.
On the other hand, a thermosetting protective film-forming film can be sufficiently cured by heating even if the film is thick, and therefore a protective film having high protective performance can be formed. Further, by using a general heating apparatus such as a heating oven, a plurality of protective film forming films can be collectively heated to be thermally cured.
Therefore, in the present embodiment, it is desirable that the curable component be thermosetting. That is, the protective film forming film is preferably thermosetting.
Whether or not the protective film forming film is thermosetting can be judged in the following manner. First, a normal temperature (23 ℃) protective film forming film is heated to a temperature exceeding the normal temperature, and then cooled to the normal temperature, to prepare a heated and cooled protective film forming film. Next, when the hardness of the heated and cooled protective film forming film is compared with the hardness of the protective film forming film before heating at the same temperature, the case where the heated and cooled protective film forming film is harder is judged as the protective film forming film being thermosetting.
As the thermosetting component, for example, epoxy resin, thermosetting polyimide resin, unsaturated polyester resin, and a mixture thereof are preferably used. The thermosetting polyimide resin is a generic name of a polyimide precursor and a thermosetting polyimide which can be thermally cured to form a polyimide resin.
An epoxy resin as a thermosetting component has a property of forming a three-dimensional network structure and forming a firm coating film when heated. As such an epoxy resin, various known epoxy resins can be used. In the present embodiment, the molecular weight (formula weight) of the epoxy resin is preferably 300 or more and less than 50000, 300 or more and less than 10000, 300 or more and less than 5000, 300 or more and less than 3000. In addition, the epoxy equivalent of the epoxy resin is preferably 50 to 5000g/eq, more preferably 100 to 2000g/eq, and further preferably 150 to 1000 g/eq.
Specific examples of the epoxy resin include glycidyl ethers of phenols such as bisphenol a, bisphenol F, resorcinol, phenyl novolac (phenyl novolac), and cresol novolac; glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidyl-type or alkylglycidyl-type epoxy resins obtained by substituting active hydrogen bonded to a nitrogen atom such as aniline isocyanurate (aniline isocyanurate) with a glycidyl group; vinylcyclohexane diepoxide, 3, 4-epoxycyclohexylmethyl-3, 4-bicyclohexane carboxylate, 2- (3, 4-epoxy) cyclohexyl-5, 5-spiro (3, 4-epoxy) cyclohexane-m-dioxane, and the like, so-called alicyclic epoxy oxides in which an epoxy group is introduced by, for example, oxidation or the like of a carbon-carbon double bond in a molecule. Further, an epoxy resin having a biphenyl skeleton, a dicyclohexyldiene skeleton, a naphthalene skeleton, or the like can also be used.
When a thermosetting component is used as the curable component (B), it is preferable to use the curing agent (C) together as an auxiliary. As the curing agent for epoxy resin, a heat-active latent epoxy resin curing agent is preferable. The "thermally active latent epoxy resin curing agent" refers to a type of curing agent which is not easily reacted with an epoxy resin at normal temperature (23 ℃) and is activated by heating at a certain temperature or higher to react with the epoxy resin. As a method for activating a heat-active latent epoxy resin curing agent, there are: a method of generating active species (anion, cation) using a chemical reaction based on heating; a method of stably dispersing in an epoxy resin at around normal temperature, compatibly-dissolving with the epoxy resin at high temperature and starting a curing reaction; a method of starting a curing reaction after dissolving out a molecular sieve-encapsulated type curing agent at a high temperature; microcapsule-based methods, and the like.
Among the above-mentioned methods, a method of stably dispersing in an epoxy resin at around room temperature, and starting a curing reaction by being compatible with and dissolved in the epoxy resin at high temperature is preferable.
Specific examples of the thermally active latent epoxy resin curing agent include various onium salts, dibasic acid dihydrazide compounds, dicyandiamide, amine adduct curing agents, high-melting-point active hydrogen compounds such as imidazole compounds, and the like. These heat-reactive latent epoxy resin curing agents may be used singly or in combination of two or more. Dicyandiamide is particularly preferred in this embodiment.
Further, as a curing agent for the epoxy resin, a phenol resin is also preferable. As the phenol resin, there can be used, without particular limitation, a polycondensate of a phenol such as an alkylphenol, a polyphenol, or naphthol, and an aldehyde. Specifically, phenol novolac resin, o-cresol novolac resin, p-cresol novolac resin, t-butylphenol novolac resin, dicyclopentadiene cresol resin, poly-p-vinylphenol resin, bisphenol a-type novolac resin, modified products thereof, and the like can be used.
The phenolic hydroxyl group contained in these phenolic resins can be easily subjected to addition reaction with the epoxy group of the epoxy resin by heating, and a cured product having high impact resistance can be formed.
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, or 0.3 to 10 parts by mass, based on 100 parts by mass of the epoxy resin. When the content of the curing agent (C) is in the above range, the protective film can easily provide the performance of protecting the work.
When dicyandiamide is used as the curing agent (C), it is more preferable to use the curing accelerator (D) together. As the curing accelerator, imidazoles (imidazoles in which one or more hydrogen atoms are substituted with a group other than a hydrogen atom) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-dimethyloimidazole, 2-phenyl-4, 5-dimethyloimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferable. Among them, 2-phenyl-4, 5-dimethylol imidazole 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, or 0.3 to 10 parts by mass, based on 100 parts by mass of the epoxy resin. When the content of the curing accelerator (D) is within the above range, the protective film can easily provide the performance of protecting a workpiece.
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, 9 to 40 parts by mass, or 10 to 30 parts by mass, based on 100 parts by mass of the total weight of the protective film forming composition. When the thermosetting component and the curing agent are blended in such a ratio, the performance of protecting the work as a protective film can be easily obtained.
(2.2.3 energy ray-curable component)
When the curable component (B) is an energy ray-curable component, the energy ray-curable component is preferably uncured, preferably adhesive, and more preferably uncured and adhesive.
The energy ray-curable component is a component that is cured by irradiation with an energy ray, and is a component for imparting film formability, flexibility, and the like to the protective film.
As the energy ray-curable component, for example, a compound having an energy ray-curable group is preferable. Examples of such a compound include known compounds.
(2.2.4 Filler)
By incorporating the filler (E) into the protective film forming film, the thermal expansion coefficient of the protective film obtained by forming the protective film forming film into a protective film can be easily adjusted. By making the thermal expansion coefficient close to that of the workpiece, the adhesion reliability with the workpiece is further improved. Further, by incorporating the filler (E) into the protective film forming film, a hard protective film can be easily obtained to obtain a performance of protecting a work, and the moisture absorption rate of the protective film can be reduced.
The filler (E) may be either an organic filler or an inorganic filler, and is preferably an inorganic filler in view of shape stability at a high temperature such as 260 ℃.
Examples of preferable inorganic fillers include powders of silica, alumina, talc, calcium carbonate, red iron oxide, silicon carbide, boron nitride, and the like; beads obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, and the like. Among them, silica and surface-modified silica are preferable. 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 size of the filler is preferably 0.02 to 10 μm, 0.05 to 5 μm, or 0.10 to 3 μm.
When the average particle diameter of the filler is in the above range, the workability of the composition for forming a protective film is improved. As a result, the composition for forming a protective film and the quality of the protective film-forming film are easily stabilized.
In addition, unless otherwise specified, "average particle diameter" in the present specification means a value of a particle diameter (D50) at a cumulative value of 50% in a particle size distribution curve obtained by a laser diffraction scattering method.
The content of the filler is preferably 15 to 80 parts by mass, 30 to 75 parts by mass, 40 to 70 parts by mass, or 45 to 65 parts by mass, based on 100 parts by mass of the total weight of the composition for forming a protective film.
When the lower limit of the content of the filler is set to the above value, the viscosity of the protective film forming film is easily reduced, and therefore the above-mentioned probe viscosity value is easily controlled. When the upper limit of the content of the filler is set to the above value, the adhesion between the protective film forming film and the work is improved, and the adhesion between the protective film and the work is appropriately improved.
(2.2.5 coupling agent)
The protective film-forming film preferably contains a coupling agent (F). By containing the coupling agent, after the protective film forming film is cured, the adhesion between the protective film and the work can be improved without impairing the heat resistance of the protective film, and the water resistance (moist 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 gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropylmethyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma- (methacryloyloxypropyl) trimethoxysilane, gamma-aminopropyltrimethoxysilane, N-6- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropylmethyldimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-hydroxysilane, beta-hydroxysilane, and the like-hydroxysilane, Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like. These silane coupling agents may be used singly or in combination of two or more.
(2.2.6 colorant)
The protective film forming film preferably contains a colorant (G). Therefore, the back surface of the workpiece such as a chip can be shielded, various electromagnetic waves generated in the electronic device can be blocked, and the malfunction of the workpiece such as a chip can be reduced. In the step of removing the outer protective film forming film of the punching blade from the first release film to obtain the inner protective film forming film of the punching blade on the first release film, it is immediately determined by the naked eye whether or not the inner protective film forming film to be left is accidentally peeled and removed.
As the colorant (G), for example, known pigments such as inorganic pigments, organic pigments, and organic dyes can be used. In the present embodiment, inorganic pigments are preferable.
Examples of the 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) pigments, ATO (antimony tin oxide) pigments, and the like. 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 amount of the colorant (particularly carbon black) to be blended in the protective film-forming film may vary depending on the thickness of the protective film-forming film, and when the thickness of the protective film-forming film is 20 μm, for example, the amount of the colorant to be blended is preferably 0.01 to 10 mass%, 0.04 to 7 mass%, or 0.07 to 4 mass% with respect to the total mass of the protective film-forming film.
The average particle diameter of the colorant (especially carbon black) is preferably 1 to 500nm, particularly preferably 3 to 100nm, and further preferably 5 to 50 nm. When the average particle diameter of the colorant is within the above range, the light transmittance can be easily controlled to a desired range.
(2.2.7 other additives)
The protective film-forming composition may further contain, for example, a photopolymerization initiator, a crosslinking agent, a plasticizer, an antistatic agent, an antioxidant, a gettering agent, a tackifier, a release agent, and the like as other additives within a range not to impair the effects of the present invention.
Among them, the content of the release agent in the composition for forming a protective film is preferably less than a predetermined amount. In the present embodiment, the content of the release agent is preferably less than 0.00099 mass% with respect to the total mass of the protective film forming film. If the content of the release agent is too large, the adhesion reliability between the protective film and the work tends to be lowered. Examples of the release agent include alkyd based release agents, silicone based release agents, fluorine based release agents, unsaturated polyester based release agents, polyolefin based release agents, and wax based release agents.
(3. first Release film)
The first release film is a film capable of supporting the protective film forming film in a peelable manner. When the cutout is formed in the protective film forming sheet, the cutout reaches a part of the first release film so as not to penetrate through the first release film. That is, when the cutout is formed in the protective film forming sheet, the first release film is half-cut (half cut).
The first release film may be composed of one layer (single layer) or two or more layers of the base material, and the surface of the base material may be subjected to a release treatment from the viewpoint of controlling 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.
In this embodiment, the first release film preferably has a base material and a first release agent layer. By having the first release agent layer, the physical properties of the surface of the first release film on which the first release agent layer is formed can be easily controlled.
In the first release film, the first release agent layer is preferably formed directly on the surface of the base material. By forming the first release agent layer directly on the surface of the substrate, the production of the first release film becomes easy, and therefore, cost reduction can be achieved.
In this embodiment, the first release agent layer is formed on the surface of the first release film on the protective film-forming film side. As shown in fig. 4, in the protective film forming sheet 1, the first release film 20 includes the base 21 and the first release agent layer 22, and 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 thickness of the first release film is not particularly limited, but is preferably 30 μm to 100 μm. The thickness of the first release film is more preferably 40 μm or more, and still more preferably 45 μm or more. The thickness of the first release film is more preferably 80 μm or less, and still more preferably 70 μm or less.
When the protective film forming film is cut with the dicing blade, the lower limit value of the thickness of the first release film is set to the above value, and thus the dicing blade can be prevented from penetrating the first release film and cutting the first release film. Further, before the protective film forming sheet is unwound and the protective film forming film is cut out and conveyed to the next step, the protective film forming sheet passes through a roller such as a guide roller in the apparatus, and the upper limit value of the thickness of the first release film is set to the above value, whereby the protective film forming film can be prevented from being peeled from the first release film.
The thickness of the first release film is the thickness of the entire first release film. For example, the thickness of the first release film composed of a plurality of layers means the total thickness of all the layers constituting the first release film.
(surface modulus of elasticity of first Release film at 3.123 ℃)
In the present embodiment, the surface elastic modulus of the surface of the first release film in contact with the protective film forming film at 23 ℃ (hereinafter, also referred to as the surface elastic modulus of the first release film at 23 ℃) is 17MPa or less. The surface elastic modulus is an index of the ease of surface deformation. As shown in fig. 3D, when the surface elastic modulus of the first release film at 23 ℃ is within the above range, the surface 20b (e.g., the first release agent layer) of the first release film 20 in contact with the protective film forming film easily follows the deformation of the protective film forming film 10 when the dicing blade 50 is pulled out. As a result, the protective film forming film 10 can be inhibited from peeling off from the first release film 20 to form a float.
The surface elastic modulus of the surface of the first release film in contact with the protective film forming film at 23 ℃ is preferably 15MPa or less, 14MPa or less, 13MPa or less, or 12MPa or less. The lower limit of the surface elastic modulus of the surface of the first release film in contact with the protective film forming film at 23 ℃ is not particularly limited, but in the present embodiment, it is preferably 3MPa or more, 4MPa or more, or 5MPa or more.
The surface elastic modulus of the surface of the first release film in contact with the protective film forming film at 23 ℃ can be measured using an atomic force microscope with a cantilever. That is, the cantilever was pressed and pulled away from the surface of the first release film in contact with the protective film forming film, and a force curve was obtained. And fitting the obtained force curve by using a formula of a JKR theory to obtain the elastic modulus, wherein the elastic modulus is used as the surface elastic modulus of the invention. The specific measurement method will be described in detail in the examples below.
In the present embodiment, the product of the probe tack value (mN) of the protective film forming film at 23 ℃ and the surface elastic modulus (MPa) of the surface of the first release film in contact with the protective film forming film at 23 ℃ is 66000 or less. By setting the volume to 66000 or less, the formation of floating due to the peeling between the protective film forming film and the first release film can be suppressed.
The product of the probe viscosity (mN) of the protective film forming film at 23 ℃ and the surface elastic modulus (MPa) of the surface of the first release film contacting the protective film forming film at 23 ℃ is preferably 60000 or less, and more preferably 54000 or less.
When the first release film has the base material and the first release agent layer, the first release agent layer is a surface of the first release film which is in contact with the protective film forming film, as described above. Therefore, the surface elastic modulus of the first release agent layer may be within the above range.
In the protective film forming sheet of this embodiment, when the peeling force with which the first peeling film is peeled off from the protective film forming film is F1 and the peeling force with which the second peeling film is peeled off from the protective film forming film, which will be described later, is F2, F1 and F2 satisfy the relationship of F1 > F2. By satisfying such a relationship, when the second release film is removed from the protective film forming sheet, the protective film forming film 11 to be left is not removed together with the second release film, and the protective film forming film 11 is easily left on the first release film.
Thus, the first release film is a heavy release film and the second release film is a light release film.
F1 is preferably 50mN/100mm or more, 70mN/100mm or more, 90mN/100mm or more, 110mN/100mm or more, and preferably 130mN/100mm or more. When F1 is in the above range, the formation of floating due to the peeling between the protective film forming film and the first release film can be further suppressed.
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 examples below.
Hereinafter, a case where the first release film includes a base material and a first release agent layer will be described.
(3.2 base Material)
The base material of the first release film is not particularly limited as long as it can support the protective film forming film before the protective film forming film is stuck to the workpiece, and is generally composed of a film (hereinafter referred to as "resin film") mainly made of a resin-based material.
As specific examples of the resin film, a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene vinyl acetate copolymer film, an ionomer resin film, an ethylene- (meth) acrylic acid copolymer film, an ethylene- (meth) acrylate copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, and the like can be used. In addition, crosslinked films of these films may also be used. Further, a laminated film of these films is also possible. In the present embodiment, a polyethylene terephthalate film is preferable from the viewpoint of environmental safety, cost, and the like.
The base material may contain various additives such as a colorant, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler in the resin film.
The thickness of the base material is not particularly limited, and is within the range of the thickness of the first release film, which can function appropriately in each step using the protective film-forming sheet. The thickness of the substrate is preferably 30 μm to 100 μm. The thickness of the base material is more preferably 40 μm or more, and still more preferably 45 μm or more. The thickness of the base material is more preferably 80 μm or less, and still more preferably 70 μm or less.
(3.3 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 made of a material that can impart releasability. In this embodiment, the first release agent layer can be obtained by curing a composition for a first release agent layer containing silicone.
The thickness of the first release agent layer is not particularly limited, but is preferably 30nm to 200 nm. The thickness of the first release agent layer is more preferably 50nm or more, and still more preferably 80nm or more. Further, the thickness of the first release agent layer is more preferably 180nm or less.
When the thickness of the first release agent layer is within the above range, stable release performance can be exhibited when the protective film-forming film is attached to a workpiece.
(3.4 composition for first Release agent layer)
In the present embodiment, examples of the composition for the first release agent layer include alkyd-based release agents, silicone-based release agents, fluorine-based release agents, unsaturated polyester-based release agents, polyolefin-based release agents, and wax-based release agents, and among them, silicone-based release agents are preferable. When the composition for the first release agent layer contains a silicone release agent, the composition preferably contains a silicone release agent and a heavy release additive.
(3.4.1 Silicone-based 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.
The silicone may be any of an addition reaction type, a polycondensation reaction type, and an energy ray curing type such as an ultraviolet curing type and an electron beam curing type, and is preferably an addition reaction type silicone. Addition reaction type silicone has high reactivity and excellent productivity, and has advantages such as less change in peeling force after production and no curing shrinkage as compared with polycondensation type silicone.
Specific examples of the addition reaction type silicone include organopolysiloxanes having 2 or more alkenyl groups having 2 to 10 carbon atoms such as vinyl, allyl, propenyl, and hexenyl groups at the end and/or side chain of the molecule. In addition, from the viewpoint of reducing the surface elastic modulus, it is preferable that the number of alkenyl groups in the addition reaction type silicone is small.
The content of the silicone composed of dimethylpolysiloxane is preferably less than 100 parts by mass, less than 90 parts by mass, less than 80 parts by mass, or less than 70 parts by mass, based on 100 parts by mass of the total weight of the composition for the first release agent layer (excluding a catalyst described later).
When such an addition reaction type silicone is used, it is preferable to use a crosslinking agent and a catalyst together.
Examples of the crosslinking agent include an organopolysiloxane having at least 2 hydrogen atoms bonded to silicon atoms in 1 molecule.
Specific examples of the crosslinking agent include dimethylhydrogensiloxy end-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy end-blocked methylhydrogensiloxane, poly (hydrogensilsesquioxane), and the like.
In addition, from the viewpoint of reducing the surface elastic modulus, the content of the crosslinking agent in the composition for the first release agent layer is preferably small.
Examples of the catalyst include platinum group metal compounds such as fine particulate platinum, fine particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, and rhodium.
By using the catalyst, the curing reaction of the composition for the first release agent layer can be more effectively performed.
The content of the silicone release agent is preferably 30 to 100 parts by mass or 50 to 100 parts by mass, based on 100 parts by mass of the total weight of the composition for a first release agent layer (excluding the catalyst), from the viewpoint of the surface elastic modulus being within the above range and the viewpoint of the release force F1 being within the above range.
(3.4.2 heavy Release additive)
The heavy release additive is used to increase the release force F1 of the first release film from the protective film forming film. Examples of the heavy release additive include organic silanes such as silicone resins and silane coupling agents, and among them, silicone resins are preferably used.
As the silicone resin, for example, those containing siloxane units [ R ] as monofunctional groups are preferably used3SiO1/2]With as tetrafunctional siloxane units [ SiO ]4/2]The MQ resin of Q unit of (1). In addition, 3R in the M unit each independently represent a hydrogen atom, a hydroxyl group, or an organic group. From the viewpoint of easily suppressing the silicone transfer, 1 or more of 3R in the M unit is preferably a hydroxyl group or a vinyl group, and more preferably a vinyl group.
The content of the heavy release additive is preferably 0 to 50 parts by mass, 5 to 45 parts by mass, or 10 to 40 parts by mass, based on 100 parts by mass of the total weight of the composition for a first release agent layer (excluding the catalyst).
Among them, from the viewpoint of reducing the surface elastic modulus, it is preferable that the content of the silicone resin (particularly, MQ resin) in the composition for the first release agent layer is small.
The composition for the first release agent layer may contain a commonly used additive in the release agent layer within a range not to impair the effects of the present invention. Examples of such additives include dyes and dispersants.
(4. second Release film)
The second release film is a film capable of supporting the protective film forming film in a releasable manner. In the case where the cut is formed in the protective film forming sheet, the cut penetrates the second release film, and when a laminate of the protective film forming film having the closed shape and the first release film is formed, the second release film is removed together with the protective film forming film other than the protective film forming film having the closed shape.
The second release film may be composed of one layer (single layer) or two or more layers of the base material, and the surface of the base material may be subjected to a release treatment from the viewpoint of controlling 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.
In addition, when the second release agent layer is formed, the second release agent layer is formed on the surface of the second release film on the protective film formation film side. As shown in fig. 4, in the protective film forming sheet 1, the second release film 30 has a base material 31 and a second release agent layer 32, and the main surface 30b of the second release agent layer 32 is in contact with the main surface 10b of the protective film forming film.
The thickness of the second release film is not particularly limited, but is preferably 10 μm to 75 μm. The thickness of the second release film is more preferably 18 μm or more, and still more preferably 24 μm or more. The thickness of the second release film is more preferably 60 μm or less, and still more preferably 45 μm or less. From the viewpoint of making the peel force F2 and the peel force F1F 1 > F2 as described above, the thickness of the second release film is preferably equal to or less than the thickness of the first release film, and more preferably smaller than the thickness of the first release film.
The thickness of the second release film is the thickness of the entire second release film. For example, the thickness of the second release film composed of a plurality of layers means the total thickness of all the layers constituting the second release film.
(4.1 base Material)
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.
(4.2 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 it is made of a material capable of imparting releasability. For example, the second release agent layer can be obtained by curing a composition for the second release agent layer containing silicone, as in the first release agent layer.
The second composition for a release agent layer can be selected from the materials exemplified in the first composition for a release agent layer, as long as the relationship between F1 and F2 is satisfied. Among them, the content of the material exemplified as the heavy release additive is preferably less than the content in the composition for the first release agent layer or is not contained.
(5. method for producing protective film-forming sheet)
The method for producing the protective film-forming sheet of the present embodiment is not particularly limited, and a known method can be used. For example, first, compositions for a release agent layer (a composition for a first release agent layer and a composition for a second release agent layer) for forming a first release film and a second release film are prepared. In the present embodiment, from the viewpoint of adjusting the viscosity to improve the coatability to the substrate, it is preferable to apply a coating agent obtained by diluting the composition for a release agent layer containing each component described above with a diluent solvent to the substrate.
Examples of the diluting solvent include aromatic hydrocarbons such as toluene, fatty acid esters such as ethyl acetate, ketones such as methyl ethyl ketone, and organic solvents such as aliphatic hydrocarbons such as hexane and heptane. These diluting solvents may be used alone or in combination of two or more.
The solid content concentration of the coating agent containing the composition for the first 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% by mass. The coating agent containing the composition for the second release agent layer has the same solid content concentration as the coating agent containing the composition for the first release agent layer.
In this embodiment, after a coating agent containing the composition for the first release agent layer is applied to one surface of the base material, the coating film is dried and cured to form the first release agent layer. Thereby obtaining a first release film. The second release film can also be produced in the same manner.
Next, a composition for forming a protective film forming film was prepared. In the same manner as in the composition for a release agent layer, in the present embodiment, it is preferable to apply a coating agent obtained by diluting the composition for forming a protective film with a diluent solvent to the release film. The type of the diluting solvent may be the same as that of the composition for a release agent layer.
On the other hand, 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.
In this embodiment, a coating agent containing the composition for forming a protective film is applied to 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, and then heated and dried to form a coating film. Next, a second release agent layer of a second release film or a first release agent layer of a first release film is laminated on the coating film, thereby producing a protective film-forming sheet. In the present embodiment, from the viewpoint of making the peeling force F1 within the above range and from the viewpoint of making F1 > F2, it is preferable that the coating agent comprising the composition for forming a protective film is applied to the first release agent layer of the first release film, not to the second release agent layer.
Examples of the coating method of the coating agent containing each composition include spin coating, spray coating, bar coating, blade coating, roll blade coating, die coating, and gravure coating.
(6. method for manufacturing device)
As an example of a method for manufacturing a device using the protective film forming sheet of the present embodiment, a method for manufacturing a chip with a protective film obtained by processing a wafer to which a protective film forming film is attached will be described.
First, as shown in fig. 5, the protective film forming sheet 1 is unwound from the roll of the protective film forming sheet 1, and a long protective film forming sheet 1 is prepared. Next, as shown in fig. 5 and 2B, a slit 40 that penetrates the second release film 30 and the protective film forming film 10 and reaches a part of the first release film 20 is formed in the long protective film forming sheet by using a dicing blade 50.
By forming the slit 40, the circular protective film forming film 11 can be obtained. In the protective film-forming sheet 1, the probe tack value of the protective film-forming film at 23 ℃ is less than 6200mN, the surface elastic modulus of the surface of the first release film in contact with the protective film-forming film at 23 ℃ is 17MPa or less, and the product of the probe tack value and the surface elastic modulus is 66000 or less, so that, as shown in fig. 3C, the formation of floating due to the peeling between the protective film-forming film 10 and the first release film 20 can be suppressed when the dicing blade 30 is pulled out. That is, in the circular protective film forming film 11, the maximum value D of the distance from the end face of the protective film forming film 11 to the portion where floating is observed is less than 4 mm. Further, the trace of the protective film forming film 10 due to the peeling of the protective film forming film 10 and the first peeling film 20 is also suppressed.
Therefore, when the second release film 30 and the protective film forming films 12 other than the protective film forming film 11 are removed after the notch is formed, the protective film forming film 11 is not removed by being unintentionally peeled from the long first release film 20 due to lifting. That is, as shown in fig. 2C, the protective film forming sheet in which the protective film forming film 11 remains on the long first release film can be easily obtained.
Next, as shown in fig. 6A, the protective film forming film 11 is attached to the back surface 60B of the wafer 60 as a workpiece, and as shown in fig. 6B, the first release film 20 is peeled from the laminate and the protective film forming film 11 is formed into a protective film to form the protective film 15. Then, the wafer with the protective film is singulated to obtain chips with the protective film. In addition, the wafer may be singulated and then subjected to protective film formation.
Since the formation of floating on the protective film forming film can be suppressed, the surface of the protective film is also suppressed from being marked. Therefore, the chip with the protective film can be obtained, wherein appearance defects of the protective film are suppressed.
(7. modification)
In the above, the description has been given of the protective film forming sheet (fig. 1A) having a configuration in which the first release film is disposed on one surface of the protective film forming film and the second release film is disposed on the other surface thereof, but as described above, the protective film forming sheet may have a configuration without the second release film (fig. 1B).
As shown in fig. 2B, the protective film forming sheet of the present embodiment further includes a long protective film forming sheet having a slit and formed with a plurality of protective film forming films 11 to be attached to a work (fig. 2B). Further, the present invention includes a sheet roll obtained by winding the long protective film forming sheet. Further, a long protective film-forming sheet is cut into individual pieces that can form a single protective film-forming film 11 to be attached to a workpiece, and the protective film-forming sheet of the present embodiment is also included.
Further, the protective film-forming sheet of the present embodiment also includes a long-sized protective film-forming sheet which does not have the second peeling film, has a slit, and has a plurality of protective film-forming films 11 to be attached to the work formed thereon; a sheet roll formed by winding the long protective film forming sheet; and cutting the long protective film forming sheet into individual pieces capable of forming a protective film forming film 11 to be adhered to a workpiece.
In fig. 5, the protective film forming film 11 to be attached to the workpiece is circular, but may have other shapes as long as it is a closed shape. Examples of the other shapes include a polygon such as a triangle, and an ellipse. Further, it is preferable that the closed shape corresponds to the shape of the workpiece.
While the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and can be modified in various ways within the scope of the present invention.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
(preparation of first Release film)
The following components were mixed at the blending ratios (in terms of solid content) shown in table 1, and a coating agent including the composition for the first release agent layer was prepared using a mixed solvent of toluene and methyl ethyl ketone (toluene/methyl ethyl ketone: 1/1 (mass ratio)) so that the solid content concentration was 2 mass%.
(alpha) silicone release agent
[ alpha ] -1 ] Silicone-based mold release agent containing organopolysiloxane having vinyl groups and organopolysiloxane having hydrosilyl groups (manufactured BY Dow Corning Toray Co., Ltd., BY24-561, solid content 30 mass%)
(alpha-2) Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-62-1387, weight average molecular weight: 2000)
(beta) Silicone resins
MQ resin having vinyl group (SD-7292, manufactured by Dow Corning Toray Co., Ltd., solid content 71 mass%)
(gamma) catalyst
Platinum (Pt) catalyst (manufactured by Dow Corning Toray Co., Ltd., SRX-212, solid content 100% by mass)
A coating agent containing the prepared composition for forming a first release agent layer was applied to a PET film (product name: DIAFOIL (registered trademark) T-100, thickness: 50 μm, manufactured by Mitsubishi Chemical Corporation) as a substrate so that the film thickness after heating and drying was 0.15 μm, and a first release agent layer was formed on the PET film to prepare a first release film.
[ Table 1]
(preparation of second Release film)
As the second release film, a film obtained by subjecting a PET film to a release treatment ("SP-PET 381130" manufactured by Lintec Corporation, 38 μm in thickness) was used.
(production of protective film Forming film)
The following components were mixed at the blending ratios (in terms of solid content) shown in table 2, and diluted with methyl ethyl ketone so that the solid content concentration was 50 mass%, to prepare a coating agent containing the composition for forming a protective film.
(A) Polymer component
(A-1) A (meth) acrylic ester copolymer (weight-average molecular weight: 40 ten thousand, glass transition temperature: -1 ℃ C.) obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate
(A-2) a (meth) acrylic ester copolymer (weight-average molecular weight: 45 million, glass transition temperature: 2 ℃ C.) obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 65 parts by mass of methyl acrylate, 12 parts by mass of glycidyl methacrylate, and 13 parts by mass of 2-hydroxyethyl acrylate
(B) Curing component (thermosetting component)
(B-1) bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828, epoxy equivalent 184 to 194g/eq)
(B-2) acrylate rubber Fine particles dispersed bisphenol A type liquid epoxy resin (NIPPON SHOKUBAI CO., LTD., manufactured by BPA328, epoxy equivalent 230g/eq, acrylate rubber content 20phr)
(B-3) Dicyclopentadiene-based epoxy resin (EPICLON HP-7200HH, softening point 88-98 ℃ C., epoxy equivalent 255-260 g/eq)
(C) Curing agent: dicyandiamide (manufactured by Mitsubishi Chemical Corporation, DICY7)
(D) Curing accelerator: 2-phenyl-4, 5-dimethylol imidazole (manufactured by SHIKOKU CHEMICALS CORPORATION, CURIZOL 2PHZ)
(E) Filling material
(E-1) epoxy-modified spherical silica Filler (SC 2050MA, average particle diameter 0.5 μm, manufactured by Admatechs Co., Ltd.)
(E-2) silica Filler (YC 100C-MLA, average particle diameter 0.1 μm, manufactured by Admatechs Co., Ltd.)
(F) Silane coupling agent: gamma-glycidyl Ether oxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM403, methoxy equivalent 12.7mmol/g, molecular weight 236.3)
(G) Colorant: carbon black (manufactured by Mitsubishi Chemical Corporation, MA600B, average particle diameter 28nm)
The coating agent containing the prepared composition for forming a protective film was applied to the surface of the first release film on which the first release agent layer was formed, and dried at 100 ℃ for 2 minutes to form a protective film forming film having a thickness of 20 μm. Next, the peeled surface of the prepared second release film was attached to the protective film forming film, and a protective film forming sheet having release films formed on both surfaces of the protective film forming film was obtained. The attaching conditions were 60 ℃ temperature, 0.4MPa pressure, and 1 m/min speed.
The obtained protective film-forming sheet was cut into a width of 320mm and wound around a hollow plastic core having a diameter of 3 inches at a length of 10m to form a sheet roll.
Subsequently, the following measurement and evaluation were performed.
(Probe tack value of protective film Forming film at 23 ℃ C.)
From the produced protective film-forming sheet, a plurality of individual sheets on which the protective film-forming film 11 is formed are obtained. The second release film is peeled from the two sheets, and the protective film forming films are bonded to each other, thereby obtaining a laminate in which the first release film, the two protective film forming films, and the first release film are laminated in this order. The first release film was peeled from the obtained laminate, the second release film was peeled from the other sheet, and the protective film forming films were bonded to each other to obtain a laminate in which the first release film, three protective film forming films, and the first release film were laminated in this order. The above operation was repeated a predetermined number of times to obtain a measurement sample in which a first release film, a laminate of protective film forming films having a thickness of 800 μm. + -. 20 μm, and a first release film were laminated in this order.
The first release film on one side was peeled off from the obtained measurement sample, and the probe tack value of the film surface of the protective film was measured at 23 ℃ using a probe tack TESTER (stainless steel probe) manufactured by TESTER SANGYO CO. The probe was cleaned by wiping with methyl ethyl ketone prior to the assay.
The measurement conditions were as follows.
Contact load: 200gf, and,
Contact speed (Contactspeed): 10 mm/sec,
Detection area (ProbeArea): 5mm phi,
Contact time (contact): 1 minute, the,
Peel speed (Peelingspeed): 10 mm/sec.
The measurement was performed 7 times while changing the contact position of the probe on the protective film formation film surface. The smallest and 2 nd smallest of the 7 test values were discarded. The average of the remaining 5 test values was taken as "probe viscosity value for protective film forming film at 23 ℃ (mN). Further, ten digits of the integer of the measured value are rounded. The results are shown in Table 2.
(surface modulus of elasticity of first Release film at 23 ℃ C.)
A cantilever of a silicon nitride material (product name: MLCT, front end radius: 20nm, resonance frequency: 125kHz, spring constant: 0.6N/m) was set on an atomic force microscope (product name: MLCT corporation, MultiMode 8). The first release film thus produced was placed on an atomic force microscope, and the surface of the first release agent layer of the first release film thus produced was pressed and pulled away at a pressing amount of 2nm and a scanning speed of 10Hz by means of a cantilever provided. The force curve obtained by this operation was fitted using the formula of JKR theory, and the surface elastic modulus was calculated. The surface elastic modulus of 4096 points was measured in 1 μm × 1 μm of the surface of the first release agent layer of the first release film, and the average value of these values was taken and rounded off one decimal point after the decimal point to obtain the surface elastic modulus (MPa). The results are shown in Table 2.
(peeling force F1 for peeling the first release film from the protective film-forming film)
The second release film was peeled from the obtained protective film-forming sheet. A laminate sample was produced by attaching a good adhesive surface of a good adhesive PET (TOYOBO co., ltd., PET25A-4100) having a thickness of 25 μm to the surface of the protective film forming film exposed by peeling, by heat lamination (70 ℃, 1 m/min). The laminate sample was cut into a width of 100mm to prepare a sample for measurement. The back surface of the first release film of the measurement sample was fixed to the hard support plate with a double-sided tape.
The protective film-forming film/well-bonded PET composite (integrated type) body was peeled from the first release film at a measurement distance of 100mm, a peel angle of 180 °, and a peel speed of 1 m/min using a universal type tensile tester (manufactured by Shimadzu Corporation, product name "AUTOGRAPH (registered trademark) AG-IS"), and the load at this time was measured. The average value of the loads between 80mm excluding the first 10mm load and the last 10mm load of the measurement distance among the measured loads was taken as the peel force F1. The results are shown in Table 2.
(peeling force for peeling the second peeling film from the protective film forming film F2)
The obtained protective film-forming sheet was cut into a width of 100mm to prepare a sample for measurement. The back surface of the first release film of the measurement sample was fixed to the hard support plate with a double-sided tape.
The second release film was peeled from the sample for measurement at a measurement distance of 100mm, a peel angle of 180 ° and a peel speed of 1 m/min using a universal type tensile tester (manufactured by Shimadzu Corporation, product name "AUTOGRAPH (registered trademark) AG-IS"), and the load at this time was measured. The average value of the loads between 80mm excluding the first 10mm load and the last 10mm load of the measurement distance among the measured loads was taken as the peel 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 punching work)
The obtained sheet for forming a protective film was subjected to punching processing (circle of 298mm inner diameter) of a protective film forming film using RAD-3600F/12 manufactured by Lintec Corporation to obtain a laminate of the protective film forming film and the first release film shown in fig. 2B. The distance between the end face and the portion where the floating between the protective film forming film and the first release film was observed in the direction from the end face of the protective film forming film toward the center of the protective film forming film was measured, and the maximum value was determined by the following criteria.
The results are shown in Table 2.
A. less than 1mm
B is more than 1 and less than 2mm
C is more than 2 and less than 4mm
D is more than 4mm
From table 2, it was confirmed that the formation of the floating was suppressed when the probe tack value of the protective film forming film at 23 ℃, the surface elastic modulus of the surface of the first release film in contact with the protective film forming film at 23 ℃, and the product of the probe tack value and the surface elastic modulus were within the above ranges.
Claims (7)
1. A protective film-forming sheet comprising a protective film-forming film and a first release film arranged so as to be peelable from one main surface of the protective film-forming film,
the probe tack value of the protective film forming film at 23 ℃ is smaller than 6200mN,
the surface elastic modulus of the surface of the first release film in contact with the protective film forming film at 23 ℃ is 17MPa or less,
the product of the probe viscosity value and the surface elastic modulus is 66000 or less.
2. The protective film-forming sheet according to claim 1, wherein the first release film comprises a base material and a first release agent layer formed on one main surface of the base material, and the first release agent layer is in contact with the protective film-forming film.
3. The protective film-forming sheet according to claim 1 or 2, which comprises a second release film that is arranged so as to be peelable on the other main surface of the protective film-forming film,
when the peeling force for peeling the first release film from the protective film forming film is F1 and the peeling force for peeling the second release film from the protective film forming film is F2, F1 and F2 satisfy the relationship of F1 > F2.
4. A protective film-forming sheet according to any one of claims 1 to 3, wherein the first release agent layer has a thickness in the range of 30nm to 200 nm.
5. The protective film forming sheet according to any one of claims 1 to 4, wherein a notch is formed in the protective film forming sheet so that a part of the protective film forming sheet has a predetermined closed shape when the protective film forming sheet is viewed in a plan view,
the slit penetrates the protective film forming film in a thickness direction of the protective film forming sheet and reaches a part of the first release film.
6. The protective film forming sheet according to claim 5, wherein a maximum value of a distance between an end surface of the protective film forming film having the closed shape and a portion where a float formed between the protective film forming film and the first release film is observed is less than 4mm in a direction from the end surface toward a center of the protective film forming film.
7. A method for processing a protective film-forming sheet, comprising a step of forming a notch so that a part of the protective film-forming sheet according to any one of claims 1 to 4 has a predetermined closed shape,
the slit penetrates the protective film forming film in a thickness direction of the protective film forming sheet and reaches a part of the first release film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020-136431 | 2020-08-12 | ||
| JP2020136431A JP2022032554A (en) | 2020-08-12 | 2020-08-12 | Protective film forming sheet and processing method for protective film forming sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114075419A true CN114075419A (en) | 2022-02-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110737279.1A Pending CN114075419A (en) | 2020-08-12 | 2021-06-30 | Protective film forming sheet and method for processing protective film forming sheet |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2022032554A (en) |
| KR (1) | KR20220021415A (en) |
| CN (1) | CN114075419A (en) |
| TW (1) | TW202206279A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2024007757A (en) * | 2022-07-06 | 2024-01-19 | 日東電工株式会社 | Protective sheet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017145735A (en) | 2016-02-17 | 2017-08-24 | 日立オートモティブシステムズ株式会社 | Control device for internal combustion engine and warming-up method for exhaust emission control catalyst |
-
2020
- 2020-08-12 JP JP2020136431A patent/JP2022032554A/en active Pending
-
2021
- 2021-06-30 CN CN202110737279.1A patent/CN114075419A/en active Pending
- 2021-07-30 KR KR1020210100675A patent/KR20220021415A/en active Search and Examination
- 2021-08-11 TW TW110129616A patent/TW202206279A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220021415A (en) | 2022-02-22 |
| JP2022032554A (en) | 2022-02-25 |
| TW202206279A (en) | 2022-02-16 |
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