CN114075417A - Sheet for forming protective film and method for producing same - Google Patents
Sheet for forming protective film and method for producing same Download PDFInfo
- Publication number
- CN114075417A CN114075417A CN202110735474.0A CN202110735474A CN114075417A CN 114075417 A CN114075417 A CN 114075417A CN 202110735474 A CN202110735474 A CN 202110735474A CN 114075417 A CN114075417 A CN 114075417A
- Authority
- CN
- China
- Prior art keywords
- protective film
- film
- forming
- release
- film forming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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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
- C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- 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
- 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
-
- 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
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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
- 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
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
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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
-
- 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
- C09J2301/312—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 parameters being the characterizing feature
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- 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)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dicing (AREA)
Abstract
The invention provides a sheet for forming a protective film and a manufacturing method thereof, wherein the sheet can sufficiently inhibit the defect of waste removal even when the width of a notch during punching is narrow. The sheet for forming a protective film is a long sheet and has a protective film forming film and a first release film provided on one surface of the protective film forming film, and is characterized in that the adhesion force after two protective film forming films are adhered for 2 minutes at 23 ℃ under a load of 2kgf is 19N/25mm or less.
Description
Technical Field
The present invention relates to a protective film forming sheet and a method for manufacturing the same. In particular, the present invention relates to a sheet for forming a protective film having a protective film forming film suitably used for protecting a workpiece such as a semiconductor wafer or a processed product such as a semiconductor chip obtained by processing the workpiece, and a method for producing the sheet for forming a protective film.
Background
In recent years, semiconductor devices are manufactured by a mounting method called flip chip bonding. In this mounting method, when a semiconductor chip having a circuit surface on which a convex electrode such as a bump (bump) is formed is mounted, the circuit surface side of the semiconductor chip is bonded to a chip mounting portion in an inverted (face down) manner. 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. In order to form such a protective film, an uncured resin film (hereinafter referred to as a "protective film forming film") is used as a precursor thereof. The protective film is attached to the back surface of the semiconductor wafer, and is diced together with the wafer to be formed into chips. By curing the protective film-forming film, a chip having a protective film on the back surface can be obtained.
As a product form of the protective film forming film, there is known a protective film forming sheet 10 of a two-layer structure in which a protective film forming film 11 is laminated on a first release film 12 in a peelable manner as shown in fig. 1, or a protective film forming sheet 20 of a three-layer structure in which a protective film forming film 11 is sandwiched between two release films (12, 13) as shown in fig. 3. The protective film-forming sheet is long and wound in a roll shape for storage and transportation. Such a protective film-forming sheet may be formed by punching a protective film-forming film in advance into substantially the same shape as a workpiece (a general name of an adherend such as a semiconductor wafer) and then attached to the workpiece. The protective film forming sheet thus punched is obtained by laminating a protective film forming film 16 punched into a predetermined closed shape on the first release film 12 (fig. 2) or sandwiching it between two release films 12 and 13 (fig. 4).
The punched protective film-forming sheet is manufactured by punching a protective film-forming film into a predetermined closed shape by a die, and is used so as to remove the unnecessary portion 17 around the punched protective film-forming film 16. In the case of a protective film forming sheet having a two-layer structure of the protective film forming film 11 and the first release film 12, the notch 14 is cut so that the protective film forming film 11 is completely punched out into a predetermined closed shape and the first release film 12 is not completely punched out, and the protective film forming film 16 having a predetermined closed shape is left on the first release film 12 to remove the unnecessary portion 17 in the periphery. In the case of a protective film forming sheet having a three-layer structure in which the protective film forming film 11 is sandwiched between two release films (12, 13), a notch 14 is cut so that the protective film forming film 11 and one second release film 13 are completely punched out into a predetermined closed shape and the other first release film 12 is not completely punched out, and a protective film forming film 16 having a predetermined closed shape is left on the first release film 12, and the peripheral unnecessary portion 17 and the second release film 13 are removed.
The case of the protective film forming sheet having a two-layer structure will be described in detail. As shown in fig. 5, a sheet 10 for forming a protection film, which is composed of a protection film forming film 11 and a first release film 12, is punched out to form a protection film forming sheet after punching by cutting out a notch 14 so that the protection film forming film 11 is completely punched out into a predetermined closed shape and the first release film 12 is not completely punched out. This process is called a "punching process".
Then, in order to attach the punched protective film forming sheet to a workpiece, an unnecessary portion 17 around the protective film forming film 16 punched out in a predetermined closed shape is removed (fig. 6). This process is referred to as a "scrap removal process". As a result, a laminated body having the protective film forming film 16 punched out into a predetermined closed shape on the first release film 12, which can be used for attachment to a workpiece, can be obtained.
The case of the protective film forming sheet having the three-layer structure is the same as the case of the protective film forming sheet having the two-layer structure except that another release film 13 (second release film 13) is provided on the protective film forming film 11 in the punching process, the second release film 13 is also completely punched out into a predetermined closed shape, and the second release film 13 is removed in the scrap removing process.
As the sheet for forming a protective film, it is required to be able to stably perform a punching process (operation stability). Particularly, after punching the protective film forming film, the operation stability of the scrap removing step for removing the unnecessary portion is required. More specifically, in the scrap removal step, it is required that the protective film forming film 16 to be left is not peeled off from the first release film 12 together with the unnecessary part 17 (hereinafter, referred to as "a defect in scrap removal").
In order to solve the above problem, for example, patent document 1 proposes controlling the peeling force between the peeling film and the protective film forming film to a predetermined range.
Documents of the prior art
Patent document
Patent document 1: international publication WO2017/145735
Disclosure of Invention
Technical problem to be solved by the invention
If a defect in the removal of the scrap occurs, the production line must be stopped and the defective product discarded, which lowers the productivity of the product and increases the cost. Therefore, further suppression of the defective removal of the scrap is required.
The inventors of the present invention further diligently studied the cause of the defective removal of the scrap and obtained the following findings.
The protective film forming sheet 10 passes through a plurality of rollers such as a guide roller for the purpose of controlling the tension of the protective film forming sheet after the punching process and before the scrap removing process. At this time, as shown in fig. 7, the protective film forming sheet 10 may be bent so that the upper side of the slit 14 (the surface into which the die enters) is the roller 19 side. As a result of the bending, the width of the slit 14 is narrowed at the slit portion which is substantially parallel to the short side direction of the sheet 10, and the protective film forming film 16 is slightly deformed by being pressed, which may cause contact and adhesion between the adjacent protective film forming films 16 and the unnecessary portion 17.
After passing through the roller 19, the adhered portion of the protective film forming film 16 and the unnecessary part 17 is often separated again, but may be maintained without being separated. If the scrap removal is performed in a state where the protective film forming film 16 and the unnecessary part 17 are adhered to each other, the protective film forming film 16 that should remain on the first release film 12 is accidentally peeled off from the first release film 12 together with the unnecessary part 17 to be removed, and a defect of scrap removal occurs.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a sheet for forming a protective film and a method for manufacturing the same, which can sufficiently suppress the removal of scraps even when the width of a notch in punching is narrow.
Means for solving the problems
The scheme of the invention is as follows.
(1) A protective film-forming sheet which is a long sheet and has a protective film-forming film and a first release film provided on one surface of the protective film-forming film, wherein,
the adhesion force after attaching two pieces of protective film forming films to each other at 23 ℃ for 2 minutes with a load of 2kgf is 19N/25mm or less.
(2) The protective film-forming sheet according to (1), wherein a surface elastic modulus of a surface of the first release film in contact with the protective film-forming film is 17MPa or less.
(3) The protective film forming sheet according to (1) or (2), 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.
(4) The protective film-forming sheet according to (3), wherein the width of the slit at the interface between the protective film-forming film and the first release film is 8 μm or more.
(5) A method for producing a sheet for forming a protective film by punching, comprising a step of forming a notch so that a part of the sheet for forming a protective film described in the above (1) or (2) 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.
(6) The method for producing a sheet for forming a protective film by punching according to item (5), wherein the width of the notch at the interface between the protective film forming film and the first release film is 8 μm or more.
Effects of the invention
According to the present invention, a sheet for forming a protective film and a method for manufacturing the same can be provided, which can sufficiently suppress the defective removal of scraps even when the width of a notch in punching is narrow.
Drawings
FIG. 1 is a schematic sectional view of a protective film-forming sheet according to an embodiment
Fig. 2 is a schematic cross-sectional view showing a state after punching the protective film-forming sheet of the embodiment.
Fig. 3 is a schematic sectional view of a protective film-forming sheet according to another embodiment.
Fig. 4 is a schematic sectional view showing a state after punching processing is performed on a protective film forming sheet of another embodiment.
Fig. 5 is a schematic perspective view of the protective film-forming sheet after the punching process.
Fig. 6 is a schematic perspective view showing a scrap removing process.
Fig. 7 is a sectional view showing a state in which the protective film forming sheet after the punching process passes through the roller.
Fig. 8 is a schematic cross-sectional view of an example of a chip having a protective film formed by forming a protective film of the present embodiment into a protective film.
Fig. 9 is a schematic sectional view for explaining a step of attaching the protective film forming sheet of this embodiment to a wafer.
Fig. 10 is a schematic cross-sectional view for explaining a process of singulating (singulating) a wafer with a protective film.
Fig. 11 is a schematic sectional view for explaining a step of disposing a chip with a protective film on a substrate.
Description of the reference numerals
10: a protective film-forming sheet (this embodiment); 11: forming a film by the protective film; 12: a first release film; 13: a second release film; 14: cutting; 16: forming a membrane by the protective membrane subjected to punching processing; 17: a useless portion; 19: a roller; 20: a protective film-forming sheet (another embodiment); 21: a wafer; 22: cutting the slices; 30: a chip with a protective film; 31: a chip; 32: a protective film; 33: a convex electrode; 50: a substrate.
Detailed Description
First, main terms used in the present specification will be described.
The work is a plate-like body that is attached to the protective film forming film of the present embodiment 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. As the processed product of the workpiece, for example, a wafer is singulated to obtain chips. Specifically, a semiconductor wafer is singulated to obtain semiconductor chips. At this time, the protective film is formed on the back surfaces of the wafer and the chip.
The "front surface" of a workpiece such as a wafer refers to a surface on which a circuit, a convex electrode such as a bump, and the like are formed, and the "back surface" refers to a surface on which a circuit, an electrode (for example, a convex electrode such as a bump), and the like are not 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 the same.
The release film is a film that supports the protective film forming film in a releasable manner. For the film, the thickness is not limited and is used in a concept including a sheet.
The mass ratio in the description of the composition for forming a protective film and the composition for a release agent layer is based on the effective component (solid component), and the solvent is not included unless otherwise specified.
Hereinafter, the present invention will be described in detail in the following order according to specific embodiments.
(1. protective film forming film)
As shown in fig. 1 and 5, the protective film forming sheet 10 of the present embodiment is a long sheet having a protective film forming film 11 and a first release film 12 provided on one surface of the protective film forming film 11, and is usually wound in a roll.
The protective film forming film 11 is attached to a workpiece and formed into a protective film, thereby forming a protective film for protecting the workpiece or a work of the workpiece.
The "formation of a protective film" means that the protective film forming film 11 has sufficient characteristics to protect a workpiece or a processed product of the workpiece. Specifically, when the protective film forming film of the present embodiment 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 forming film is cured, whereby the protective film can be firmly bonded to the work, and a protective film having durability can be formed.
When the protective film forming film 11 does not contain a curable component and is used in a non-cured state, the protective film forming film of the present embodiment is formed as a protective film at the time of attaching the protective film forming film to a workpiece. In other words, the protective film may also be the same as the protective film forming film.
In the case where high protective performance is not required, since it is not necessary to cure the protective film forming film, the protective film forming film may be non-curable.
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, it is more preferable that the protective film is a thermoset.
Further, the protective film-forming film preferably has adhesiveness at normal temperature (23 ℃) or preferably develops adhesiveness by heating. This enables the work and the protective film forming film to be bonded to each other when they are laminated. Therefore, positioning can be surely performed before curing the protective film forming film.
The protective film forming film may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers. When the protective film forming film has a plurality of layers, these plurality of layers may be the same as each other or different from each other, and the combination of the layers constituting these plurality of layers is not particularly limited.
In the present embodiment, it is preferable that the protective film is formed as one layer (single layer). If the protective film forming film is formed of a plurality of layers, there is a risk of interlayer peeling due to a difference in thermal expansion and contraction between layers in a process in which a temperature change occurs (at the time of reflow treatment or at the time of using a device), and this risk can be reduced if the protective film is formed of one layer.
The thickness of the protective film-forming film is not particularly limited, but is preferably 100 μm or less, more preferably 70 μm or less, further preferably 45 μm or less, and particularly preferably 30 μm or less. If the thickness of the protective film forming film is within the above range, the protective film forming film subjected to the punching process is likely to be separated again after passing through the roll even if the unnecessary part comes into contact with and adheres to the protective film forming film when passing through the roll after the punching process. The thickness of the protective film forming film is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more. If the thickness of the protective film forming film is within the above range, the protective performance of the obtained protective film becomes good.
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.
Hereinafter, a protective film formed on a chip as a work of a workpiece will be described. Specifically, a protective film formed by forming a protective film forming film into a protective film will be described with reference to the chip 30 with a protective film shown in fig. 8.
As shown in fig. 8, the chip 30 with a protective film has a protective film 32 formed on the back surface side (upper side in fig. 8) of the chip 31, and a convex electrode 33 formed on the front surface side (lower side in fig. 8) of the chip 31.
A circuit is formed on the front surface side of the chip 31, and a convex electrode 33 is formed on the front surface side so as to be electrically connected to the circuit. The chip 30 with a protective film is disposed so that the surface on which the convex electrode 33 is formed faces the chip mounting substrate. Then, the substrate is electrically and mechanically connected to the substrate through the convex electrode 33 by a predetermined heat treatment (reflow treatment), and is mounted. The convex electrode 33 may be a bump or a pillar (pillar) electrode.
(1.1 adhesion of protective films to one another)
In the present embodiment, the adhesion force when the protective film forming films constituting the protective film forming sheet are adhered to each other is controlled within a predetermined range, thereby suppressing the defect of the scrap removal. Specifically, the present embodiment is characterized in that the adhesion force after attaching two pieces of protective film forming films to each other at 23 ℃ for 2 minutes with a load of 2kgf is 19N/25mm or less. The adhesion is preferably 15N/25mm or less, more preferably 11N/25mm or less. Further, since the holding performance of the work may be deteriorated if the adhesion force is too small, the adhesion force is preferably 0.1N/25mm or more, more preferably 1N/25mm or more, and particularly preferably 3N/25mm or more. The reason why the adhesion force is measured after the protective film forming films are adhered to each other for 2 minutes is that, in the apparatus for removing scraps and adhering to a workpiece, in the step of passing the protective film forming sheet through the roller 19, the time for the cut portion to contact the roller 19 and stop is about 2 minutes.
As described above, by controlling the adhesion force between the protective film forming films within a predetermined range, even if the protective film forming sheet is bent after the punching step and the protective film forming film 16 and the unnecessary part 17 subjected to the punching adhere to each other, the protective film forming film 16 and the unnecessary part 17 can be separated again after the protective film forming sheet passes through the roller, and the defect of scrap removal can be reduced.
(1.2 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 (protective film-forming composition) is preferably a resin composition containing at least the polymer component (a), the curable component (B), and the filler (E). The polymer component is considered to be 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, the composition for forming a protective film is regarded as containing the polymer component and the curable component.
(1.2.1 Polymer component)
The polymer component (a) imparts film formability (film formability) to the protective film forming film and gives it appropriate tackiness so that the protective film forming film is surely and uniformly attached to the work. The weight average molecular weight of the polymer component is usually in the range of 5 to 200 ten thousand, preferably in the range of 10 to 150 ten thousand, and particularly preferably in the range of 20 to 100 ten thousand. When the weight average molecular weight is too low, the adhesion between the protective film-forming films tends to increase. On the other hand, if the weight average molecular weight is too high, compatibility with other components is deteriorated, and as a result, formation of a uniform film is inhibited. As such a polymer component, for example, an acrylic resin, a urethane resin (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 the present specification, unless otherwise specified, "weight average molecular weight" is a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method. As the measurement by this method, for example, a high performance column "TSK gurd column H" sequentially connected to a high performance GPC apparatus "HLC-8120 GPC" manufactured by TOSOH CORPORATION can be usedXL-H”、“TSK Gel GMHXL”、“TSK Gel G2000 HXL"(all of the above, manufactured by TOSOH CORPORATION)" was measured with a differential refractometer as a detector under conditions of a column temperature of 40 ℃ and a feed rate of 1.0 mL/min.
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. Among them, the (meth) acrylate monomer preferably includes an alkyl (meth) acrylate in which an alkyl group has 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, it is preferable to introduce a glycidyl group into the acrylic resin using glycidyl methacrylate or the like. The acrylic resin into which a glycidyl group has been introduced has high compatibility with an epoxy resin as a thermosetting component described later, and the glass transition temperature (Tg) of the protective film forming film after curing is high, thereby increasing heat resistance. In the present embodiment, it is preferable to introduce hydroxyl groups into the acrylic resin using hydroxyethyl acrylate or the like in order to control the adhesiveness to a work or the adhesive properties.
The glass transition temperature of the acrylic resin is preferably-70 ℃ to 40 ℃, more preferably-35 ℃ to 35 ℃, still more preferably-20 ℃ to 30 ℃, still more preferably-10 ℃ to 25 ℃, and particularly preferably-5 ℃ to 20 ℃. By setting the glass transition temperature of the acrylic resin to the above range, the flowability of the protective film forming film and the protective film at the time of heating can be suppressed, and thus a smooth protective film can be easily obtained. If the glass transition temperature is too low, the adhesion between the protective film-forming films tends to increase. If the glass transition temperature is too high, compatibility with other components is poor, and formation of a uniform film is prevented as a result.
When the acrylic resin has m kinds (m is an integer of 2 or more) of structural units, the glass transition temperature of the acrylic resin can be calculated as follows. That is, when any non-repeating number of 1 to m is assigned to each of the m monomers from which the structural unit in the acrylic resin is derived in order and these are named as "monomer 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 a glass transition temperature of the acrylic resin, m is an integer of 2 or more, Tgk is a glass transition temperature of a homopolymer of monomer m, Wk is a mass fraction of structural unit m derived from monomer m in the acrylic resin, and Wk satisfies the following formula.
[ mathematical formula 2]
Wherein m and Wk are the same as those described above.
As Tgk, values described in a Polymer data manual (polymers データ and ハンドブック), an adhesion manual (adhesion ハンドブック), a Polymer manual (Polymer Handbook), or the like can be used. For example, a homopolymer of methyl acrylate at Tgk ℃ at Tgk ℃ at-54 ℃ and a homopolymer of n-butyl acrylate at Tgk ℃ at 105 ℃ and a homopolymer of 2-hydroxyethyl acrylate at Tgk ℃ at-15 ℃ and a homopolymer of glycidyl methacrylate at Tgk ℃ at 41 ℃ and 2-ethylhexyl acrylate at Tgk ℃ at-70 ℃.
The content of the polymer component is preferably 5 to 80 parts by mass, more preferably 8 to 70 parts by mass, even more preferably 10 to 60 parts by mass, even more preferably 12 to 55 parts by mass, even more preferably 14 to 50 parts by mass, and particularly preferably 15 to 45 parts by mass, based on 100 parts by mass of the total weight of the protective film forming composition. By making the content of the polymer component within the above range, the amount of the low-molecular weight component that increases the adhesion of the protective film-forming films to each other can be limited to an appropriate range, thus making it easy to design the material of the composition for forming a protective film.
(1.2.2 thermosetting Components)
The curable component (B) cures the protective film forming film, thereby forming a hard protective film. As the curable component, a thermosetting component, an energy ray curable component, or a mixture thereof can be used. When the protective film of this embodiment is cured by irradiation with energy rays, the light transmittance of the protective film is reduced by the inclusion of a filler, a colorant, and the like, which will be described later. Therefore, for example, when the thickness of the protective film forming film becomes thick, the energy ray curing easily becomes insufficient.
On the other hand, even if the thickness of the thermosetting protective film forming film is increased, the film can be sufficiently cured by heating, and therefore a protective film having high protective performance can be formed. Further, by using a conventional heating apparatus such as a heating oven, a plurality of sheets of the protective film forming film can be heated at one time to be thermally cured.
Therefore, in the present embodiment, the curable component is preferably thermosetting. That is, the protective film forming film of the present embodiment 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 higher than the normal temperature, and then cooled to the normal temperature, thereby forming a heated and cooled protective film forming film. Next, the hardness of the protective film forming film after heating and cooling and the hardness of the protective film forming film before heating are compared at the same temperature, and when the protective film forming film after heating and cooling is harder, it is judged that the protective film forming film is thermosetting.
As the thermosetting component, for example, epoxy resin, thermosetting polyimide resin, unsaturated polyester resin, and a mixture of these resins are preferably used. The thermosetting polyimide resin is a generic term for a low-molecular-weight and low-viscosity monomer or precursor polymer that forms a polyimide resin by thermal curing. Non-limiting specific examples of thermosetting polyimide resins are described, for example, in the society of fiber and industry, Vol.50, No.3(1994), P106-P118.
Epoxy resins, which are thermosetting components, have the property of forming a three-dimensional network when heated, thereby forming a strong coating film. 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 such epoxy resins include glycidyl ethers of phenols such as bisphenol a, bisphenol F, resorcinol, phenol novolac (phenol novolac), cresol novolac (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 so-called alicyclic epoxides in which an epoxy group is introduced by, for example, oxidation of a carbon-carbon double bond in the molecule. In addition, epoxy resins having a biphenyl skeleton, a dicyclohexyldiene skeleton, a naphthalene skeleton, or the like may be used.
When a thermosetting component is used as the curable component (B), it is preferable to use the curing agent (C) as an auxiliary at the same time. 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" is a type which hardly reacts with an epoxy resin at normal temperature (23 ℃) but is activated by heating to a certain temperature or higher to react with the epoxy resin. As a method for activating the heat-reactive latent epoxy resin curing agent, there are a method of generating an active species (anion or cation) in a chemical reaction by heating; a method of stably dispersing in an epoxy resin at around normal temperature, but being compatible with the epoxy resin at high temperature, dissolving and initiating a curing reaction; a method of dissolving out a molecular sieve-encapsulated curing agent at a high temperature to initiate a curing reaction; microcapsule-based methods, and the like.
Among the exemplified methods, a method is preferable in which the epoxy resin is stably dispersed in the epoxy resin at around room temperature, but the epoxy resin is compatible with the epoxy resin at high temperature, and the epoxy resin is dissolved and the curing reaction is initiated.
Specific examples of the heat-active latent epoxy resin curing agent include various onium salts, dibasic acid dihydrazide compounds, dicyanodiamide, amine adduct curing agents, high-melting-point active hydrogen compounds such as imidazole compounds, and the like. These thermally active latent epoxy resin curing agents may be used alone or in combination of two or more. In the present embodiment, dicyanodiamine is particularly preferable.
Further, as a curing agent for the epoxy resin, a phenol resin is also preferable. As the phenol resin, a condensate of a phenol such as an alkylphenol, a polyphenol, or naphthol, and an aldehyde or the like can be used without particular limitation. Specifically, phenol novolac resin, o-cresol novolac resin, p-cresol novolac resin, t-butylphenol novolac resin, dicyclopentadiene cresol resin, poly-p-vinyl phenol resin, bisphenol a type novolac resin, or modified products thereof can be used.
The phenolic hydroxyl group contained in these phenolic resins can be easily subjected to an addition reaction with the epoxy group of the above 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, more preferably 0.1 to 20 parts by mass, even more preferably 0.2 to 15 parts by mass, and particularly preferably 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 network structure of the protective film becomes dense, and the performance of protecting the work as the protective film is easily obtained.
When dicyanodiamine is used as the curing agent (C), it is preferable to further use a curing accelerator (D) together. Preferred examples of the curing accelerator include imidazoles (imidazole 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. Among them, 2-phenyl-4-methyl-5-hydroxymethylimidazole is particularly preferable.
The content of the curing accelerator is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, even more preferably 0.2 to 15 parts by mass, and particularly preferably 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 in the above range, the network structure of the protective film becomes dense, and therefore, the performance of protecting a workpiece as the protective film can be easily obtained.
The total content of the thermosetting component and the curing agent is preferably 3 to 80 parts by mass, more preferably 5 to 60 parts by mass, even more preferably 7 to 50 parts by mass, even more preferably 9 to 40 parts by mass, and particularly preferably 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 the above ratio, a proper viscosity can be exhibited before curing, and a stable sticking operation can be performed. Further, after curing, the property of protecting the work as a protective film is easily obtained.
When a low-molecular-weight compound is used as the thermosetting component and the curing agent, the adhesiveness of the protective film-forming film may increase, and the adhesion between the protective film-forming films may increase. Therefore, it is preferable to select the kind of the thermosetting component and the curing agent and the blending amount thereof within the above range so as to control the viscosity to an appropriate value.
(1.2.3 energy ray-curable component)
When the curable component (B) is an energy ray-curable component, the energy ray-curable component is preferably uncured, preferably has adhesiveness, and more preferably is uncured and has adhesiveness.
The energy ray-curable component is a component that is cured by irradiation with an energy ray, and is a component for imparting film 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 energy ray-curable components.
When a low-molecular-weight compound is used as the energy ray-curable component, the adhesiveness of the protective film-forming film may increase, and the adhesion between the protective film-forming films may increase. Therefore, it is preferable to select the kind and the blending amount of the energy ray-curable component and the energy ray-curable component so as to control the viscosity to an appropriate value.
(1.2.4 Filler)
By incorporating the filler (E) into the protective film forming film, the adjustment of the thermal expansion coefficient of the protective film obtained by forming the protective film forming film into a protective film becomes easy, and by bringing the thermal expansion coefficient close to the thermal expansion coefficient of the work, the adhesion reliability of the package obtained by forming the film using the protective film is further improved. Further, by incorporating the filler (E) into the protective film forming film, a hard protective film can be obtained, the moisture absorption rate of the protective film is further reduced, and the adhesion reliability of the package is further improved.
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 high temperature.
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 filler preferably has an average particle diameter of 0.02 to 10 μm, more preferably 0.05 to 5 μm, and particularly preferably 0.10 to 3 μm.
By setting the average particle diameter of the filler to the above value, the operability of the composition for forming a protective film is improved. Therefore, the composition for forming a protective film and the quality of the protective film-forming film are easily stabilized.
Unless otherwise specified, the "average particle diameter" in the present specification refers to a value of the particle diameter (D50) at 50% of the integrated value 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, more preferably 30 to 75 parts by mass, even more preferably 40 to 70 parts by mass, and particularly preferably 45 to 65 parts by mass, based on 100 parts by mass of the total weight of the composition for forming a protective film.
By setting the content of the filler to the above value, the adhesion force of the protective film forming films to each other can be easily controlled within an appropriate range. If the content of the filler is too small, the viscosity of the protective film forming film increases, and the adhesion between the protective film forming films excessively increases. On the other hand, if the amount of the filler is too large, the shape retention of the protective film forming film may be reduced, and the film may not be able to retain its shape due to the bending on the roll, and the adhesiveness of the protective film forming film and the adhesiveness to the work may be excessively reduced.
Further, the protective film forming film preferably contains two or more kinds of filler. That is, the filler (E) is preferably a mixture of two or more fillers. The "containing two or more fillers" may contain two or more fillers having different materials, or may contain two or more fillers having different average particle diameters.
In the present embodiment, two or more types of filler having different average particle diameters are preferably contained. By including the filler having different average particle diameters in the protective film forming film, the filler having a small average particle diameter can be easily arranged in the voids of the filler having a large average particle diameter. As a result, the above-described effects can be obtained, and the adhesion of the protective film forming films to each other can be easily set within the above-described range.
When two or more fillers having different average particle diameters are contained, the average particle diameter of the filler having the largest average particle diameter is preferably 1.5 to 100 times, more preferably 2 to 20 times, and still more preferably 3 to 18 times the average particle diameter of the filler having the smallest average particle diameter.
Further, it can be confirmed whether or not the protective film or the protective film forming film contains two or more fillers having different average particle diameters by observing the cross section of the protective film or the protective film forming film.
(1.2.5 coupling agent)
The protective film-forming film preferably contains a coupling agent (F). By containing the coupling agent, the adhesion between the protective film and the work can be improved without impairing the heat resistance of the protective film after the protective film-forming film is cured, 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-glycidyloxypropylmethyldimethoxysilane, gamma-hydroxysilane, gamma-glycidyloxypropyltetrasulfide, gamma-glycidyloxypropyltrimethoxysilane, gamma-hydroxysilane-tetrasulfide-hydroxysilane-tetrasulfide-hydroxysilane-tetrasulfide-hydroxysilane-, Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like. These silane coupling agents may be used singly or in combination of two or more.
The content of the coupling agent is preferably 0.01 to 20 parts by mass, 0.1 to 10 parts by mass, 0.2 to 5 parts by mass, or 0.3 to 3 parts by mass, based on 100 parts by mass of the total weight of the composition for forming a protective film.
(1.2.6 colorant)
The protective film forming film preferably contains a colorant (G). Thus, since the back surface of the workpiece such as a chip is covered, various electromagnetic waves generated in the electronic device can be shielded, and failure of the workpiece such as a chip can be reduced. Further, when a defect in the removal of the scrap occurs, it can be immediately found by the naked eye.
As the colorant (G), for example, known colorants 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. Electromagnetic waves in a wide wavelength range can be blocked by carbon black.
The amount of the colorant (particularly, carbon black) to be blended in the protective film-forming film varies depending on the thickness of the protective film-forming film, and for example, when the thickness of the protective film-forming film is 20 μm, the content of the colorant is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and still more preferably 0.05 to 4 parts by mass, based on 100 parts by mass of the total weight of the protective film-forming composition.
The average particle diameter of the colorant (particularly carbon black) is preferably 1 to 500nm, particularly preferably 3 to 100nm, and further preferably 5 to 50 nm. If the average particle diameter of the colorant is within the above range, it is easy to control the light transmittance within a desired range.
(1.2.7 other additives)
The protective film-forming composition may contain, for example, a photopolymerization initiator, a crosslinking agent, a plasticizer, an antistatic agent, an antioxidant, a gettering agent, a thickener, 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, it 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 an alkyd-based release agent, a silicone-based release agent, a fluorine-based release agent, an unsaturated polyester-based release agent, a polyolefin-based release agent, and a wax-based release agent.
(1.2.8 control of the adhesion of protective film-forming films to each other)
As described above, the present embodiment is characterized in that the adhesion force when attaching the protective film forming films constituting the protective film forming sheet to each other is controlled within a predetermined range, and thereby the defect of the scrap removal is suppressed.
The adhesion of the protective film forming films to each other can be controlled by the kinds of the respective components constituting the protective film forming films and the blending amounts thereof.
When the weight average molecular weight of the polymer component (a) is low, the adhesion tends to increase. When the glass transition temperature of the polymer component (a) is low, the adhesion tends to increase. Further, when a low molecular weight compound is used as the curable component (B), the curing agent (C), the curing accelerator (D), and the energy ray-curable component, the adhesive force tends to increase. When the amount of the filler (E) is large, the adhesion tends to be lowered.
By partially curing the protective film forming film, the adhesion can also be controlled. For example, by partially curing the curable component (B), the adhesion can be reduced. The timing of partially curing the protective film-forming film is not particularly limited, and may be, for example, a stage before the protective film-forming sheet passes through the roller 19 in punching. However, from the viewpoint of setting the peeling forces F1 and F2 described later in an appropriate range and the viewpoint of adhesion to the workpiece, it is preferable that the protective film forming film is not partially cured as described in the examples described later.
(2. sheet for Forming protective film)
Before use, the protective film forming film may be wound up and stored in a two-layer protective forming sheet 10 in which a peelable protective film forming film 11 is laminated on a first peeling film 12, as shown in fig. 1. As shown in fig. 3, the protective film forming sheet 20 having a three-layer structure in which the protective film forming film 11 is sandwiched between two release films (the first release film 12 and the second release film 13) may be wound and stored. The release film is peeled off when the film is formed using the protective film.
The protective film forming sheet is long and wound into a roll for storage and transportation. As such a protective film-forming sheet, there is also known a protective film-forming sheet obtained by punching a protective film-forming film into substantially the same shape as a workpiece. The protective film forming film 16 punched out into a predetermined closed shape by the punching process of the protective film forming sheet thus punched out is laminated on the first release film 12 (fig. 2) or sandwiched between two release films 12 and 13 (fig. 4).
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 substrate may be modified, or a material not derived from the substrate may be formed on the surface of the substrate. In the present embodiment, it is preferable that the first release film has a base material and a release agent layer. By having the release agent layer, the physical properties of the surface of the first release film on which the release agent layer is formed can be easily controlled. In this embodiment, a coating agent containing a composition for a release agent layer described later is applied to one surface of a base material, and then the coating film is dried and cured to form a release agent layer. Thereby, a first release film was obtained.
The thickness of the first release film 12 is not particularly limited, but is preferably 30 to 100. mu.m, more preferably 40 to 80 μm, and still more preferably 45 to 70 μm.
When the lower limit of the thickness of the first release film 12 is set to the above value, it is possible to prevent the cutting blade from penetrating the first release film 12 and cutting the first release film 12 when the protective film forming film is cut with the cutting blade. Further, after the protective film forming sheet 10 is unwound and the protective film forming film 11 is cut out, the protective film forming sheet 10 passes through a roller such as a guide roller in the apparatus before being transported to the next step, but by setting the upper limit value of the thickness of the first release film 12 to the above value, the protective film forming film 11 can be prevented from being peeled from the first release film 12.
The thickness of the first release film 12 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.
Examples of the base material of the first release film 12 include a resin film and paper. Examples of the resin film include polyethylene terephthalate, polyethylene, polypropylene, polybutylene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polybutylene terephthalate, polyurethane, ethylene-vinyl acetate copolymer, ionomer resin, ethylene (meth) acrylic acid copolymer, polystyrene, polycarbonate, fluororesin, low-density polyethylene, linear low-density polyethylene, and triacetyl cellulose. Examples of the paper include high-quality paper, coated paper (coat paper), cellophane paper, and laminated paper. These base materials may be used alone or in combination of two or more. Among them, a polyethylene terephthalate film is preferable in terms of low cost and rigidity.
At least one surface (a surface laminated with the protective film forming film) of the first release film 12 may be subjected to a release treatment with the composition for a release agent layer. The thickness of the release agent layer is preferably 30nm to 200nm, and more preferably 50nm to 180 nm.
The surface elastic modulus (23 ℃) of the surface of the first release film 12 in contact with the protective film forming film 11 is preferably 17MPa or less, more preferably 14MPa or less, even more preferably 13MPa or less, and particularly preferably 12MPa or less, and the surface elastic modulus is an index of the ease of deformation of the surface. By setting the surface elastic modulus of the surface of the first release film 12 in contact with the protective film forming film 11 within the above range, the occurrence of floating (peeling of about 1 to 4 mm) between the protective film forming film 11 and the first release film 12 can be suppressed when the die is pressed and then pulled up in the punching process. This is considered to be because the surface of the first release film 12 is relatively soft, and even if there is a release pressure due to compression by the die and release thereof, the surface of the first release film follows the deformation of the protective film forming film. By suppressing the occurrence of floating, the defect of waste removal can be further reduced. The lower limit of the surface elastic modulus of the surface of the first release film 12 in contact with the protective film forming film 11 is not particularly limited, but if the surface elastic modulus is too low, the release force may increase, and therefore, it is preferable to be 3MPa
The above is more preferably 4MPa or more, and particularly preferably 5MPa or more.
The surface elastic modulus of the surface of the first release film 12 in contact with the protective film forming film 11 at 23 ℃ can be measured using an atomic force microscope equipped with a cantilever. That is, the surface of the first release film 12 in contact with the protective film forming film 11 is cantilever-pressed and separated to obtain a force curve. The obtained force curve is fitted to the JKR theoretical formula to determine the elastic modulus, which is the surface elastic modulus of the present invention. The specific measurement method will be described in detail in examples described later.
In order to set the later-described release force F1 within an appropriate range and set the surface elastic modulus of the first release film 12 within the above-described range, in the present embodiment, as the composition for a release agent layer, for example, an alkyd-based release agent, a silicone-based release agent, a fluorine-based release agent, an unsaturated polyester-based release agent, a polyolefin-based release agent, and a wax-based release agent are preferable, and among them, a silicone-based release agent is preferable, and a silicone-based release agent and a heavy release additive are particularly preferably contained.
As the silicone-based release agent, a silicone release agent in which silicone having dimethylpolysiloxane as a basic skeleton is blended can be used.
The silicone may be any of addition reaction type, condensation reaction type, ultraviolet ray curing type, electron beam curing type, and other energy ray curing type, but is preferably addition reaction type silicone. Addition reaction type silicones have the advantages of high reactivity, excellent productivity, and less change in peeling force after production and no curing shrinkage, compared with condensation reaction type silicones.
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. From the viewpoint of reducing the surface elastic modulus, the number of alkenyl groups in the addition reaction type silicone is preferably small.
The content of the silicone composed of dimethylpolysiloxane is preferably less than 100 parts by mass, more preferably less than 90 parts by mass, even more preferably less than 80 parts by mass, and particularly preferably less than 70 parts by mass, based on 100 parts by mass of the total weight of the composition for a 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 silicon atoms bonded to hydrogen atoms in one molecule. From the viewpoint of reducing the surface elastic modulus, the content of the crosslinking agent in the composition for a release agent layer is preferably small.
Specific examples of the crosslinking agent include a dimethylhydrogensiloxy end-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, a trimethylsiloxy end-blocked methylhydrogensiloxane, and poly (hydrogen silsesquioxane).
Examples of the catalyst include platinum group metal compounds such as platinum fine particles, platinum fine particles adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, rhodium and the like.
By using such a catalyst, the curing reaction of the composition for a release agent layer can be more effectively performed.
From the viewpoint of setting the surface elastic modulus within the above range and from the viewpoint of setting the peeling force F1 described later within an appropriate range, the content of the silicone-based release agent is preferably 30 to 100 parts by mass, and more preferably 50 to 100 parts by mass, when the total weight of the composition for a release agent layer (excluding the catalyst) is 100 parts by mass.
The heavy release additive serves to increase the release force F1 described later. Examples of the heavy release additive include organic silanes such as silicone resins and silane coupling agents, and among them, silicone resins are preferred.
As silicone resins, preference is given, for example, to using MQ resins which contain siloxane units [ R ] as monofunctional3SiO1/2]With the unit M as tetrafunctional siloxane unit [ SiO ]4/2]The 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. 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 a release agent layer is small.
The content of the heavy release additive is preferably 0 to 50 parts by mass, more preferably 5 to 45 parts by mass, and particularly preferably 10 to 40 parts by mass, based on 100 parts by mass of the total weight of the composition for a release agent layer (excluding the catalyst).
From the viewpoint of adjusting the viscosity and improving the coatability to the substrate, the composition for a release agent layer is preferably used as a coating agent containing a diluent solvent in addition to the above-described various active ingredients. In the present specification, the "active ingredient" refers to a component other than the diluting solvent, out of components contained in a coating agent containing a target composition.
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 concentration of the active ingredient (solid content) in the coating agent containing the composition for a 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 composition for a release agent layer may contain an additive generally used in a release agent layer within a range not to impair the effects of the present invention. Examples of such additives include dyes and dispersants.
In the protective film-forming sheet 10 of the present embodiment, the protective film-forming film 11 is preferably punched into a predetermined shape. That is, it is preferable that the protective film forming sheet has a notch 14 formed therein so that a part of the protective film forming sheet 10 has a predetermined closed shape when the protective film forming sheet 10 is viewed in a plan view. In addition, from the viewpoint that the protective film forming film does not overflow from the work when the protective film forming film is attached to the work, the shape of the protective film forming film after punching is preferably smaller than the shape of the work.
(3. method for producing sheet for Forming protective film)
The method for producing the protective film-forming film is not particularly limited. The film can be produced using a coating agent containing the above composition for forming a protective film. The coating agent can be prepared by mixing the components constituting the composition for forming a protective film by a known method.
The protective film-forming sheet 10 of the present embodiment having the protective film-forming film 11 on the first release film 12 can be obtained by applying the obtained coating agent onto the release surface of the first release film 12 using a coater such as a roll coater, a knife coater, a roll coater, an air knife coater, a die coater, a bar coater, a gravure coater, or a curtain coater and drying the coating agent. Alternatively, a coating agent may be applied to another resin film and dried, and the obtained protective film forming film may be transferred to the first release film. In order to obtain the protective film-forming sheet 20 according to another embodiment, the second release film 13 is laminated on the exposed surface of the protective film-forming film 11 laminated with the first release film 12, and the protective film-forming sheet 20 in which the protective film-forming film 11 is sandwiched between two release films is obtained.
(4. method for producing protective film-forming sheet by punching)
A method of punching the protective film forming sheet 10 to obtain the protective film forming film 16 punched in a predetermined closed shape on the first release film 12 will be described.
(4.1 punching working procedure)
First, the protective film forming sheet 10 shown in fig. 1 is prepared without punching. The notch 14 is cut out from the surface of the protective film forming sheet 10 on the protective film forming film 11 side by a die (not shown) so as to penetrate through the protective film forming film 11 and reach a part of the surface of the first release film 12. The operation of cutting an incision without completely cutting it in such a manner as to reach a part of the surface is called half-cut (half-cut). As a result, the cutout 14 is formed in a part of the surface of the protective film forming sheet 10 so as to have a predetermined closed shape (see fig. 2 and 5). Here, when the protective film forming film is transferred onto the semiconductor wafer, the predetermined closed shape is substantially the same shape as the wafer. That is, the notch 14 is formed so as to have substantially the same shape as the shape of the workpiece to which the protective film forming film 11 is attached or the shape of the region where the protective film is to be formed. This process is called a "punching process".
The protective film forming film 11 is divided into a protective film forming film 16 punched into a predetermined closed shape and a continuous unnecessary portion 17 around the protective film forming film 16 by a punching process. The protective film forming film 16 punched out into a predetermined closed shape is provided at a plurality of positions in the longitudinal direction of the protective film forming sheet 10.
In the punching step, a known die can be used as appropriate. The punching process is performed by half-cutting so as to completely cut the protective film forming film 11 and not completely cut the first release film 12.
As shown in fig. 2 and 4, the cross-sectional shape of the slit 14 is substantially wedge-shaped, and the width of the slit 14 is wider on the upper surface side of the protective film forming film 11 into which the die enters and is narrowed on the lower surface side (the interface between the protective film forming film 11 and the first release film 12). The width D of the notch 14 is not particularly limited, but the width D of the notch 14 in the lower surface portion of the protective film forming film 11 (i.e., the upper surface portion of the first release film 12) is preferably 8 μm or more, more preferably 10 μm or more, further preferably 15 μm or more, and particularly preferably 20 μm or more, from the viewpoint of preventing contact and adhesion between the protective film forming film 16 subjected to punching and the unnecessary portion 17, or from the viewpoint of shortening the time for contact and adhesion. The width D may be measured by cutting the protective film forming sheet in the thickness direction and measuring the width of the cut in the upper surface portion of the first release film 12 in the cross section as the width D. The upper limit of the width D is not particularly limited, but is usually 100 μm or less, preferably 80 μm or less, more preferably 60 μm or less, and still more preferably 40 μm or less, in view of the width of a dicing blade capable of reliably cutting the protective film forming film. In order to form such a slit 14, a die having a cutting blade with a wide blade width at the tip end is preferably used as the die.
Through the above steps, the protective film forming sheet 10 subjected to punching processing can be obtained. In the protective film forming sheet, the notch 14 is formed so that a part of the protective film forming sheet has a predetermined closed shape (for example, a shape substantially equal to the planar shape of the semiconductor wafer) when the protective film forming sheet 10 subjected to the punching process is viewed from the top surface of the protective film forming film 11 in plan view, and the notch 14 reaches a part of the first peeling film 12 in the thickness direction of the protective film forming sheet 10. That is, a notch is also formed on the surface of the first release film 12 that contacts the protective film forming film 11. By making the dicing blade reach the first peeling film 12, the protective film forming film 11 can be completely cut off.
(4.2 waste removal Process)
The protective film forming sheet 10 passes through a plurality of rollers such as a guide roller for the purpose of controlling the tension of the protective film forming sheet after the punching process and before the scrap removing process.
As shown in fig. 6, in the scrap removing step, the continuous unnecessary portion 17 is peeled off from the first release film 12, and the protective film forming film 16 subjected to the punching process is left on the first release film 12. The stripped unnecessary part 17 is wound around a waste extracting roller.
According to the protective film forming sheet 10 of the present embodiment, since the adhesion force between the protective film forming films is low, even if the protective film forming film 16 subjected to the punching process comes into contact with and adheres to the unnecessary part 17 after passing through the roller 19 or the like after the punching process, the protective film forming film 16 and the unnecessary part 17 can be separated again after passing through the roller. As a result, the defect of scrap removal in the scrap removal step can be suppressed.
The punched protective film-forming sheet 10 can be stored and transported in a roll form.
(5. method of processing work)
As an example of a method for processing a workpiece using a sheet for forming a protective film subjected to punching processing according to the present embodiment, a method for manufacturing a package in which a chip with a protective film obtained by processing a wafer having a film formed thereon with a protective film is disposed on a substrate will be described.
The method for manufacturing the device of the present embodiment includes at least the following steps 1 to 9.
Step 1: a step of punching the protective film forming sheet 10
And a step 2: passing the punched protective film forming sheet between rollers
Step 3: removing unnecessary portion 17 of protective film forming sheet 10
And step 4: attaching the protective film forming film 11 of the protective film forming sheet 10 to the back surface of the wafer
Step 5: forming the attached protective film into a protective film
Step 6: step 7 of peeling the first release film from the protective film or the protective film forming film: singulating the wafer having the protective film or the protective film forming film on the back surface thereof into individual chips to obtain a plurality of chips each having the protective film or the protective film forming film
Step 8: disposing a chip having a protective film or a protective film-forming film on a substrate
Step 9: heating a chip with a protective film or a protective film forming film disposed on a substrate and the substrate
The steps 1 to 3 are as described above. Step 5 may be performed before step 6, or may be performed after any one of steps 6 to 9. That is, the step of forming the protective film into a protective film may be performed at any stage after the protective film forming film is attached to the wafer.
A method for manufacturing the device having the steps 1 to 9 will be described with reference to the drawings.
Fig. 2, 4, and 5 show the outline of the step 1 as described above. Fig. 6 shows an outline of step 3.
As shown in fig. 9, the protective film forming film 11 of the protective film forming sheet 10 is attached to the back surface of the wafer 21 (step 4). Then, the attached protective film forming film 11 is formed into a protective film to form a protective film 32 (step 5), and a wafer with a protective film is obtained. When the protective film forming film 11 is thermosetting, the protective film forming film 11 may be heated at a predetermined temperature for an appropriate time. When the protective film forming film 11 is energy ray-curable, an energy ray-transmitting film may be used as the first release film 12, and energy rays may be incident from the first release film 12 side.
The curing of the protective film forming film 11 may be performed after a dicing step described later, or the protective film forming film 11 may be cured after picking up a chip with the protective film forming film from a dicing sheet.
Then, the wafer 21 with the protective film is transferred onto a known dicing sheet 22, and the wafer 21 with the protective film is diced to obtain chips 31 (chips 30 with the protective film) having the protective film 32 as shown in fig. 10 (step 7). Then, the dicing sheet 22 is spread in the planar direction as necessary, and the chip 30 with the protective film is picked up from the dicing sheet 22 by a suction nozzle (not shown) or the like.
The picked-up chip 30 with the protective film may be transported to the next step, or may be temporarily stored in a tray, a tape, or the like, and transported to the next step after a predetermined period.
As shown in fig. 11, the chip 30 with the protective film transferred to the next step is transferred onto a substrate 50 by a suction nozzle, and a terminal portion on the substrate is separated from the suction nozzle and is arranged at a position where a convex electrode 33 such as a bump and a terminal portion such as a pad can be connected (step 8). In this case, a chip different from the chip 30 with the protective film may be mounted on the substrate 50. Therefore, a plurality of chips can be mounted on the substrate.
The chip with the protective film disposed at a predetermined position on the substrate is subjected to a heat treatment (reflow treatment) (step 9). The reflow treatment conditions are preferably, for example, a maximum heating temperature of 180 to 350 ℃ and a reflow time of 2 to 10 minutes.
In the reflow process, the protruding electrodes 33 of the chip 30 with a protective film are melted and electrically and mechanically connected to the terminal portions on the substrate, and the chip 30 with a protective film is mounted on the substrate.
(6. modification)
While the embodiment of the present invention has been described above by taking as an example a protective film forming sheet having a two-layer structure in which the protective film forming film 11 is provided on the first release film 12, the second release film 13 may be laminated on the exposed surface of the protective film forming film 11. That is, the protective film forming sheet may be a protective film forming sheet 20 (see fig. 3 and 4) in which the protective film forming film 11 is sandwiched between the first release film 12 and the second release film 13. In this case, the second release film 13 may be peeled off before the protective film forming film 11 is attached to the work.
The material and preferred form of the protective film forming film 11 of the protective film forming sheet 20 are the same as those in the above embodiment, and the first release film 12 is also the same as that in the description of the above embodiment.
Further, in the present embodiment, in the protective film forming sheet 20, when the peeling force when peeling the first peeling film 12 from the protective film forming film 11 is F1 and the peeling force when peeling the second peeling film 13 from the protective film forming film 11 is F2, F1 and F2 preferably satisfy the relationship of F1 > F2. By satisfying such a relationship, when the second release film 13 is removed from the protective film forming sheet 20, the protective film forming film 16 to be left is not removed together with the second release film 13, the protective film forming film 16 is likely to remain on the first release film 12, and the defect of scrap removal can be further suppressed.
Therefore, the first release film 12 is a heavy release film having a strong peeling force, and the second release film 13 is a light release film having a weak peeling force.
The peeling force F1 is preferably 50mN/100mm or more, more preferably 70mN/100mm or more, still more preferably 90mN/100mm or more, still more preferably 110mN/100mm or more, and particularly preferably 130mN/100mm or more. When F1 is in the above range, the protective film forming film 11 and the first release film 12 can be inhibited from being unintentionally peeled.
The adjustment of the release force can be controlled by, for example, the kind of the composition for a release agent layer, the thickness of the release agent layer, and the like. The second release film 13 is designed to have a lower peel force than the first release film 12. When the second release film 13 has a release agent layer, the release agent layer is not particularly limited as long as it is made of a material that can impart releasability. For example, the release agent layer of the second release film 13 can be obtained by curing a composition for a release agent layer containing silicone, as in the release agent layer of the first release film 12.
The composition for the release agent layer of the second release film 13 can be selected from the materials exemplified in the first release film 12 as long as it satisfies the relationship between F1 and F2 described above. Among them, the material exemplified as the heavy release additive is preferably contained in a smaller amount or not contained in the first release film 12.
The thickness of the second release film 13 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 setting the peel force F2 and the peel force F1 to F1 > F2 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 less 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.
As described in the embodiment, the method of manufacturing the protective film forming sheet 20 may be such that the second release film 13 is laminated on the exposed surface of the protective film forming film 11 laminated on the first release film 12.
The protective film forming sheet 20 is the same as the above embodiment except that a die is inserted from the second release film 13 side to cut the protective film forming film 11 and the second release film 13 into a predetermined closed shape when punching. As a result, the protective film forming film 11 and the second release film 13 subjected to the punching process are obtained on the first release film 12. The protective film forming sheet 20 subjected to the punching process can be wound in a roll shape for storage and transportation.
In the scrap removing step, the second release film 13 and the unnecessary portion 17 are removed by simultaneously winding the second release film 13 and the unnecessary portion 17. At this time, the second release film 13 after the punching process and the complete cutting is bonded again by using a long adhesive tape, and the second release film 13 is easily removed. As a result, the protective film forming film 16 cut into a predetermined closed shape remains on the first release film 12.
While the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments at all, and various modifications can be made within the scope of the present invention.
Examples
The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples.
(production of protective film Forming sheet)
[ first Release film (heavy Release film) ]
< coating agent containing composition for releasing agent layer >
The following composition raw materials for a release agent layer were prepared.
Silicone-based mold release agent containing organopolysiloxane having vinyl groups and organopolysiloxane having hydrosilyl groups (produced BY Dow Corning Toray Co., Ltd., BY24-561, solid content 30 mass%)
Dimethylpolysiloxane (weight average molecular weight: 2000) (manufactured by Shin-Etsu Chemical Co., Ltd., X-62-1387 (solid content: 100% by mass))
MQ resin having vinyl group as a heavy release additive (SD-7292, manufactured by Dow Corning Toray Co., Ltd., with a solid content of 71 mass%)
Platinum (Pt) catalyst (manufactured by Dow Corning Toray Co., Ltd., SRX-212, solid content 100 mass%)
The above-described raw materials were added to a mixed solvent of toluene and methyl ethyl ketone (toluene/methyl ethyl ketone: 1/1 (mass ratio)) at a blending ratio (in terms of solid content) described in table 1, and the total solid content was adjusted to 2 mass%, thereby preparing a coating agent containing a composition for a release agent layer.
< production of first Release film >
A coating agent containing a composition for a release agent layer was applied to a PET film (product name: DIAFOIL (registered trademark) T-100, thickness: 50 μm, manufactured by Mitsubishi Chemical Corporation) so that the film thickness after drying became 0.15 μm, and heating and drying were performed to form a release agent layer on the PET film, thereby manufacturing first release films (heavy release films) A to C.
< measurement of surface elastic modulus >
The surface elastic modulus of the release-treated surface of the obtained first release film was measured in the following manner.
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 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. This operation was carried out at 23 ℃. The force curve obtained by this operation was fitted based on the JKR theoretical formula, and the surface elastic modulus was calculated. As for the surface elastic modulus, 4096 points were measured in 1 μm × 1 μm of the surface of the release agent layer of the first release film, and the average value of these values was taken and one digit after the decimal point was rounded off as the surface elastic modulus (MPa). The results are shown in Table 1.
[ Table 1]
[ second Release film (light Release film) ]
"SP-PET 381130 (thickness 38 μm)" manufactured by Lintec Corporation was used.
[ coating agent containing composition for forming protective 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 became 50 mass%, to prepare coating agents.
(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 ten thousand, 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 type epoxy resin (jER 828, epoxy equivalent 184 to 194g/eq, manufactured by Mitsubishi Chemical Corporation)
(B-2) acrylic rubber Fine particle-dispersed bisphenol A type liquid epoxy resin (manufactured by Nippon Shokubai Co., Ltd., BPA328, epoxy equivalent of 230g/eq, acrylic rubber content of 20phr)
(B-3) dicyclopentadiene type epoxy resin (EPICLON HP-7200HH, softening point 88-98 ℃, epoxy equivalent 255-260 g/eq, manufactured by DIC CORPORATION)
(C) Curing agent: dicyandiamide (manufactured by Mitsubishi Chemical Corporation, DICY7)
(D) Curing accelerator: 2-phenyl-4, 5-dihydroxymethylimidazole (Curezol 2PHZ, manufactured by SHIKOKU CHEMICALS CORPORATION)
(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" having an average particle diameter of 0.1. mu.m, 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)
[ Table 2]
The prepared composition for forming a protective film was applied to the release-treated surface of the first release film (any one of the above-mentioned a to C), and dried at 100 ℃ for 2 minutes to form a protective film-forming film having a thickness of 20 μm. Then, a second release film was attached to the protective film forming film, and a protective film forming sheet having a three-layer structure in which release films were formed on both surfaces of the protective film forming film was obtained. As the attaching conditions, the temperature was 60 ℃, the pressure was 0.4MPa, and the speed was 1 m/min. Then, the protective film-forming sheet was cut into a width of 208mm and wound into a length of 50m to form a roll body.
The following measurement and evaluation were performed using the obtained protective film-forming sheet.
[ adhesion of protective film-forming films to each other ]
The protective film forming films were exposed from the protective film forming sheet in the following manner, and the protective film forming films were attached to each other, and adhesion was measured.
< fixing of protective film-forming film on adhesive tape >
I. The second release film of the protective film forming sheet of the three-layer structure of the second release film/protective film forming film/first release film was peeled off.
An adhesive tape (product name PET50PL シン: acrylic adhesive layer/50 μm PET substrate) manufactured by Lintec Corporation was attached to the exposed protective film-forming film at 23 ℃ to prepare a laminate sample of "PET substrate/acrylic adhesive layer/protective film-forming film/first release film".
Cut laminate samples into strips 25mm wide and 250mm long.
< fixing of protective film-forming film on SUS plate >
I. A double-sided tape having a PET film as a core was attached to the entire surface of an SUS plate (0.5mm thickness. times.70 mm. times.150 mm).
Peeling off the second release film of the protective film forming sheet of the three-layer structure of the second release film/the protective film forming film/the first release film.
And III, attaching the exposed protective film forming film to the entire surface of the adhesive surface of the double-sided tape to obtain a laminate sample of SUS plate/double-sided tape/protective film forming film/first release film.
And IV, stripping the first stripping film to expose the protective film forming film.
< measurement of adhesion >
The first release film was peeled from the laminate sample of "PET substrate/acrylic adhesive layer/protective film forming film/first release film" to expose the protective film forming film. The laminate of "PET substrate/acrylic adhesive layer/protective film forming film" and the laminate of "SUS plate/double-sided tape/protective film forming film" were laminated so that the protective film forming films were opposed to each other, and were bonded at 23 ℃.
The adhesive force was measured by the following measurement method after 2 minutes (± 20 seconds) had passed after the application while the adhesive force was kept still without heating.
Using a universal type tensile tester (manufactured by Shimadzu Corporation, product name)
"AUTOGRAPH AG-IS"), the peel force was measured at a peel speed of 300 mm/min, a temperature of 23 ℃ and a peel angle of 180 DEG for a measurement distance of 70 mm. The average of the measurement values between 50mm from which the first 10mm and the last 10mm of the measurement distance were removed was taken as "adhesion force between the protective film forming films".
[ peeling force F1 when peeling the first peeling film from the protective film-forming film ]
The second release film was peeled from the obtained protective film-forming sheet. A good adhesive surface of a well-adhered PET (PET 25A-4100, manufactured by TOYOBO Co., Ltd.) having a thickness of 25 μm was attached to the surface of the protective film forming film exposed by peeling by heat lamination (70 ℃ C., 1 m/min) to prepare a laminate sample. 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 sample for measurement was fixed to a hard support plate using a double-sided tape.
Using a universal type tensile tester (manufactured by Shimadzu Corporation, product name)
"AUTOGRAPH (registered trademark) AG-IS"), the protective film-forming film/well-bonded PET composite (integrated type) body was peeled from the first release film at a peeling angle of 180 ° and a peeling speed of 1 m/min, and the load at this time was measured. The measurement distance was 100mm in total, and the average of the measurement values between 80mm excluding the first 10mm and the last 10mm was taken as the peel force F1. The results are shown in Table 2.
[ peeling force F2 when peeling the second peeling film from the protective film-forming film ]
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 sample for measurement was fixed to a hard support plate using a double-sided tape.
Using a universal type tensile tester (manufactured by Shimadzu Corporation, product name)
"AUTOGRAPH (registered trademark) AG-IS"), and the second release film was peeled from the sample for measurement, and the load at that time was measured under the same conditions as those for the measurement of F1, and was used as a peeling force F2.
The obtained peel forces F1 and F2 were compared, and it was confirmed that F1 was greater than F2 for all the samples.
[ punching and scrap removal for protective film-forming sheet ]
A die was inserted from the second release film side of the protective film forming sheet using RAD-3600F/12 manufactured by Lintec Corporation in a specification for 200mm wafers, and the protective film forming film and the second release film were punched out in a circular shape (inner diameter: 198 mm). At this time, the first release film is cut so as to be incompletely punched (punching step). The four kinds of dies having different blade widths of the cutter are used to perform half-cuts having different notch widths. The punching process was performed 40 times.
After the punching process, the protective film forming sheet is moved between the plurality of rollers. Then, the portion punched out in a circular shape is left on the first release film, and the second release film and the peripheral unnecessary portion of the portion punched out in a circular shape are removed (scrap removal step). At this time, the second release film after the punching process and the complete cutting is bonded again by a long adhesive tape, and the second release film is removed.
< notch Width >
The protective film-forming sheet after the scrap removal step was cut in the thickness direction so that the cut portion of the first release film was not deformed, the protective film-forming sheet was kept flat, and the cross section was observed with a scanning electron microscope (SEM, "VE-9800" manufactured by KEYENCE CORPORATION). The width of the cut remaining on the first release film at the interface between the first release film and the protective film forming film was measured.
The 20 th circle is selected from the 40 circle parts, and measurement is performed at 6 points (regular hexagon if the points are connected) at equal intervals on the circumference of the circle. The minimum of the 6 points was taken as the "incision width". And rounding off the decimal place one digit after the decimal point.
The wider the slit width is, the more smoothly the waste removal can be performed without the protective film forming films adhering to each other.
< evaluation of scrap removability >
In the scrap removing step, the number of the protective film forming films of the circular portions among the 40 circular portions included in the scrap removing step, which were floated together with the unnecessary portions, was counted. The smaller the number of floating pieces, the less the protective film forming films are adhered to each other, and the more smoothly the scrap can be removed.
The results are summarized in Table 3.
[ Table 3]
As can be seen from table 3, when the adhesion force between the protective film forming films is 19N or less, the protective film forming films do not adhere to each other after the punching process, and the scrap removal can be smoothly performed. Further, as shown in example 7, when the width of the notch is narrowed, the protective film forming films adhere to each other after the punching process, and the scrap removal tends not to be smoothly performed.
Industrial applicability
As described above, according to the present invention, it is possible to provide a sheet for forming a protective film and a method for manufacturing the sheet, which can sufficiently suppress the removal of scraps even when the width of a notch in punching is narrow.
Claims (6)
1. A protective film-forming sheet which is a long sheet and has a protective film-forming film and a first release film provided on one surface of the protective film-forming film, wherein,
the adhesion force after attaching two pieces of protective film forming films to each other at 23 ℃ for 2 minutes with a load of 2kgf is 19N/25mm or less.
2. The protective film-forming sheet according to claim 1, wherein a surface elastic modulus of a surface of the first release film in contact with the protective film-forming film is 17MPa or less.
3. The protective film-forming sheet according to claim 1 or 2,
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.
4. The protective film-forming sheet according to claim 3, wherein the width of the cut at the interface between the protective film-forming film and the first release film is 8 μm or more.
5. A method for producing a sheet for forming a protective film by punching, comprising a step of forming a notch so that a part of the sheet for forming a protective film according to claim 1 or 2 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.
6. The method of manufacturing a sheet for forming a protective film by punching according to claim 5, wherein the width of the notch at the interface between the protective film forming film and the first release film is 8 μm or more.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020136453A JP2022032570A (en) | 2020-08-12 | 2020-08-12 | Protective film forming sheet and manufacturing method thereof |
| JP2020-136453 | 2020-08-12 |
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| Publication Number | Publication Date |
|---|---|
| CN114075417A true CN114075417A (en) | 2022-02-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110735474.0A Pending CN114075417A (en) | 2020-08-12 | 2021-06-30 | Sheet for forming protective film and method for producing same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2022032570A (en) |
| KR (1) | KR20220020780A (en) |
| CN (1) | CN114075417A (en) |
| TW (1) | TW202218869A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603077B (en) | 2016-02-24 | 2020-12-29 | 琳得科株式会社 | Adhesive sheet and method of using the same |
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2020
- 2020-08-12 JP JP2020136453A patent/JP2022032570A/en active Pending
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2021
- 2021-06-30 CN CN202110735474.0A patent/CN114075417A/en active Pending
- 2021-08-06 KR KR1020210104044A patent/KR20220020780A/en active Search and Examination
- 2021-08-11 TW TW110129617A patent/TW202218869A/en unknown
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| TW202218869A (en) | 2022-05-16 |
| KR20220020780A (en) | 2022-02-21 |
| JP2022032570A (en) | 2022-02-25 |
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