CN111849377A - Composite sheet for forming protective film - Google Patents

Composite sheet for forming protective film Download PDF

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Publication number
CN111849377A
CN111849377A CN202010317354.4A CN202010317354A CN111849377A CN 111849377 A CN111849377 A CN 111849377A CN 202010317354 A CN202010317354 A CN 202010317354A CN 111849377 A CN111849377 A CN 111849377A
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China
Prior art keywords
protective film
forming
film
meth
composite sheet
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Granted
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CN202010317354.4A
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Chinese (zh)
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CN111849377B (en
Inventor
佐伯尚哉
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Lintec Corp
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Lintec Corp
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • 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
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)

Abstract

The present invention provides a composite sheet for forming a protective film, which comprises a support sheet and a protective film-forming film provided on one surface of the support sheet, wherein the protective film-forming film has a transmittance of light having a wavelength of 365nm of 0.3% or less.

Description

Composite sheet for forming protective film
Technical Field
The present invention relates to a composite sheet for forming a protective film. The present application claims priority based on japanese patent application 2019-086700 filed in japan on 26.4.2019, and the contents thereof are incorporated herein by reference.
Background
In a process of manufacturing a semiconductor device, a work to be processed to obtain an object may be protected with a protective film.
For example, in the manufacture of a semiconductor device to which a mounting method called a flip-chip (face down) method is applied, a semiconductor wafer having an electrode such as a bump on a circuit surface is used as a workpiece, and a protective film is sometimes used to protect a back surface of the semiconductor wafer or a semiconductor chip on the side opposite to the circuit surface in order to suppress generation of cracks in the semiconductor wafer or the semiconductor chip as a divided object thereof. In the manufacturing process of a semiconductor device, a semiconductor device panel described later is used as a work, and in order to suppress the occurrence of bending or cracking in the panel, any part of the panel is sometimes protected with a protective film.
In order to form the protective film, for example, a composite sheet for forming a protective film is used which comprises a support sheet and a film for forming a protective film on one surface of the support sheet.
The protective film-forming film may function as a protective film by curing the film, or may function as a protective film in an uncured state. The support sheet can be used for fixing a workpiece provided with a film for forming a protective film or a cured product thereof. For example, when a semiconductor wafer is used as a workpiece, the support sheet can be used as a dicing sheet necessary for dividing the semiconductor wafer into semiconductor chips. Examples of the support sheet include a support sheet having a base material and an adhesive layer provided on one surface of the base material, a support sheet composed of only a base material, and the like. When the support sheet includes the adhesive layer, the adhesive layer is disposed between the base material and the protective film-forming film in the protective film-forming composite sheet.
In the case of using the above-described composite sheet for forming a protective film, first, a film for forming a protective film in the composite sheet for forming a protective film is attached to a target position of a workpiece.
Then, the workpiece in the state provided with the composite sheet for forming a protective film is processed as necessary, thereby obtaining a workpiece processed product. For example, when a semiconductor wafer is used as a workpiece, after the composite sheet for forming a protective film is adhered to the back surface of the workpiece through the film for forming a protective film, at appropriate timings: formation of the protective film by curing the protective film-forming film, cutting of the protective film-forming film or the protective film, dicing (dicing) from the semiconductor wafer to the semiconductor chip, picking up of the semiconductor chip having the cut protective film-forming film or protective film on the back surface (the semiconductor chip with the protective film-forming film or the semiconductor chip with the protective film) from the support sheet, and the like. When the semiconductor chip with the film for forming a protective film has been picked up, the semiconductor chip with the film for forming a protective film is made into a semiconductor chip with a protective film by curing the film for forming a protective film, and finally a semiconductor device is manufactured using the semiconductor chip with a protective film. Then, in any stage before obtaining the target semiconductor device, there is a case where a surface of the film for forming a protective film or a cured product thereof opposite to the surface to be stuck to the workpiece or the workpiece (that is, a surface on the side of the support sheet in the composite sheet for forming a protective film) is irradiated with laser light to perform printing (laser printing). The print can be used, for example, to identify a workpiece or workpiece having a protective film. Since the same state can be maintained even after the protective film is formed by curing the protective film, the printing applied to the protective film forming film can be performed at any stage of the protective film forming film and the cured product thereof.
Patent document 1 discloses a back surface protective film for protecting the back surface of a semiconductor element, the back surface protective film having a parallel light transmittance of 800nm or more of 15%. Further, patent document 2 discloses a composite sheet for forming a protective film, which has a total light transmittance of 3% or more at a wavelength of 555 nm.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-213244
Patent document 2: japanese patent laid-open publication No. 2016-213243
Disclosure of Invention
Technical problem to be solved by the invention
As the composite sheet for forming a protective film, in addition to a composite sheet for forming a protective film having a support sheet provided with an adhesive layer which is cured by heating, a support sheet provided with an adhesive layer which is cured by irradiation with an energy ray such as ultraviolet ray is used.
On the other hand, when the semiconductor chip or the semiconductor chip with the protective film is irradiated with the energy ray, the semiconductor chip may be broken or malfunction may occur. In particular, when an energy ray-curable adhesive is used for a semiconductor chip with a protective film, the risk is further increased because energy rays must be irradiated.
In recent years, semiconductor wafers have become thinner, and it is necessary to easily pick up semiconductor chips from a supporting sheet so as not to damage the chips.
Further, when the film for forming a protective film transmits visible light, grinding marks of the semiconductor wafer may be observed, which may impair design properties. In addition, if laser printing for process control applied to the back surface of the semiconductor wafer, which is unnecessary at the time of shipment, can be seen through the protective film-forming film or the protective film, it is seen that the laser printing overlaps with information laser-printed on the surface of the protective film-forming film, and a reading failure may be caused.
The back surface protective film disclosed in patent document 1 is capable of improving the transmittance of parallel rays having a wavelength of 800nm in order to enable a crack of a semiconductor chip to be photographed through the back surface protective film by an infrared camera, and does not disclose a composite sheet for forming a protective film which is capable of protecting the semiconductor chip under energy rays and enabling the semiconductor chip to be easily picked up from a support sheet without being damaged.
Further, the composite sheet for forming a protective film disclosed in patent document 2 is improved in total light transmittance at a wavelength of 555nm in order to enable detection of a notch of a semiconductor wafer when the composite sheet for forming a protective film is attached to the semiconductor wafer, and does not disclose a composite sheet for forming a protective film which is capable of protecting a semiconductor chip under energy rays and easily picking up the semiconductor chip from a support sheet without breaking it.
The invention aims to provide a composite sheet for forming a protective film, which is provided with a support sheet and a film for forming a protective film arranged on one surface of the support sheet, and can prevent a semiconductor chip or the semiconductor chip with the protective film from being damaged or causing misoperation even if the semiconductor chip or the semiconductor chip with the protective film is irradiated with energy rays.
Further, the present invention is directed to a composite sheet for forming a protective film, which can easily pick up a semiconductor chip from a support sheet without damaging the semiconductor chip when the semiconductor chip is picked up from the support sheet.
Further, an object of the present invention is to provide a composite sheet for forming a protective film, which is excellent in design and has a low possibility of causing a reading failure of laser printing on the surface of the protective film, because it is suppressed that grinding marks on the back surface of a wafer or laser printing applied for process management can be visually observed.
Means for solving the problems
The present invention provides a composite sheet for forming a protective film, which comprises a support sheet and a protective film-forming film provided on one surface of the support sheet, wherein the protective film-forming film has a transmittance of light having a wavelength of 365nm of 0.3% or less.
In the composite sheet for forming a protective film of the present invention, it is preferable that the support sheet includes a base material and an adhesive agent layer provided on one surface of the base material, the adhesive agent layer is disposed between the base material and the film for forming a protective film, and the adhesive agent layer is an energy ray-curable adhesive agent layer.
In the composite sheet for forming a protective film of the present invention, the transmittance of the protective film-forming film for light having a wavelength of 555nm is preferably 5% or less.
In the composite sheet for forming a protective film of the present invention, the transmittance of the film for forming a protective film for light having a wavelength of 800nm is preferably less than 20%.
Effects of the invention
According to the present invention, there can be provided a composite sheet for forming a protective film, which comprises a support sheet and a film for forming a protective film provided on one surface of the support sheet, and which does not damage a semiconductor chip or cause an erroneous operation even when the semiconductor chip or the semiconductor chip with the protective film is irradiated with an energy ray.
Further, according to the present invention, there can be provided a composite sheet for forming a protective film, which comprises a support sheet and a film for forming a protective film provided on one surface of the support sheet, and which can easily pick up a semiconductor chip from the support sheet without damaging the semiconductor chip when the semiconductor chip is picked up from the support sheet.
Further, according to the present invention, it is possible to provide a composite sheet for forming a protective film, which is excellent in design property and has a low possibility of causing a reading failure of laser printing on the surface of the protective film, because it is suppressed that grinding marks on the back surface of a wafer or laser printing applied for process management can be visually observed.
Drawings
Fig. 1 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 4 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 5 is a sectional view schematically illustrating an example of a method for manufacturing a semiconductor chip with a protective film when the composite sheet for forming a protective film according to the embodiment of the present invention is used.
Fig. 6 is a sectional view schematically illustrating an example of a method for manufacturing a semiconductor chip with a protective film when the composite sheet for forming a protective film according to the embodiment of the present invention is used.
Fig. 7 is a sectional view schematically illustrating an example of a method for manufacturing a semiconductor chip with a protective film when the composite sheet for forming a protective film according to the embodiment of the present invention is used.
Fig. 8 is a sectional view schematically illustrating an example of a method for manufacturing a semiconductor chip with a protective film when the composite sheet for forming a protective film according to the embodiment of the present invention is used.
Fig. 9 is a sectional view schematically illustrating an example of a method for manufacturing a semiconductor chip with a protective film when the composite sheet for forming a protective film according to the embodiment of the present invention is used.
Description of the reference numerals
101. 102, 103, 104: a composite sheet for forming a protective film; 1011: a protective film-forming composite sheet in which the protective film-forming film is cured; 1012: a protective film-forming composite sheet in which a protective film-forming film is cured and printed; 10. 20, 30: a support sheet; 10a, 20a, 30 a: one face (first face) of the support sheet; 13. 23: a protective film-forming film; 13': a protective film (a cured product of a protective film-forming film); 130': a cut protective film (a cured product of the cut protective film-forming film); 9: a semiconductor wafer; 9 a: a circuit forming surface of a semiconductor wafer; 9 b: a back side of the semiconductor wafer; 9': a semiconductor chip; l: and (4) laser.
Detailed Description
Diamond compact for forming protective film
A composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet and a protective film-forming film provided on one surface of the support sheet, and the protective film-forming film has a transmittance of 0.3% or less for 365nm wavelength light (which may be abbreviated as "light (365 nm)" in the present specification). By setting the transmittance of light (365nm) to 0.3% or less, even when the semiconductor chip or the semiconductor chip with the protective film is irradiated with the energy ray, the semiconductor chip is not broken or the malfunction is not caused.
Preferably, the support sheet of the composite sheet for forming a protective film according to one embodiment of the present invention includes a base material, and an adhesive agent layer provided on one surface of the base material, the adhesive agent layer being disposed between the base material and the film for forming a protective film, and the adhesive agent layer being an energy ray-curable adhesive agent layer.
The film for forming a protective film in the composite sheet for forming a protective film of the present embodiment may be curable or non-curable.
In the present specification, even after the protective film-forming film is cured, as long as the laminated structure of the support sheet and the cured product of the protective film-forming film can be maintained, the laminated structure is referred to as a "protective film-forming composite sheet".
In the present specification, unless otherwise specified, a cured product of the protective film-forming film is referred to as a "protective film".
The composite sheet for forming a protective film of the present embodiment may have another layer not belonging to any of the base material, the adhesive layer, the intermediate layer, the film for forming a protective film, and the release film, within a range not impairing the effects of the present invention.
The type of the other layer is not particularly limited, and may be arbitrarily selected according to the purpose.
The position, shape, size, and the like of the other layer may be arbitrarily selected depending on the type thereof, and are not particularly limited, but the size of the protective film-forming film or the protective film is preferably larger than the size of the workpiece to be bonded of the protective film-forming composite sheet of the present embodiment.
The thickness of the workpiece to be bonded with the composite sheet for forming a protective film of the present embodiment is not particularly limited, but is preferably 30 to 1000 μm, and more preferably 70 to 400 μm, from the viewpoint of facilitating the processing (e.g., division) of the workpiece to be described later.
The composite sheet for forming a protective film of the present embodiment is used for bonding to a workpiece, and a preferable workpiece to be bonded is, for example, a semiconductor wafer. The composite sheet for forming a protective film is preferably used for attaching to the back surface of a semiconductor wafer.
The object to which the composite sheet for forming a protective film is attached does not include a workpiece after a processing operation. The "workpiece after the machining operation" includes a target workpiece and a workpiece in a state in which machining is not completed. Examples of the workpiece in a state in which machining is not completed include a workpiece in process, a workpiece in which machining is attempted but a part of the workpiece is in an incomplete state. As the workpiece in a state in which the processing is not completed, for example, a workpiece in which an attempt is made to divide a semiconductor wafer into semiconductor chips is included, and a part of the workpiece is in a state in which the division is incomplete.
Fig. 1 is a cross-sectional view schematically showing an example of a composite sheet for forming a protective film according to an embodiment of the present invention.
The composite sheet 101 for forming a protective film shown therein is composed of a support sheet 10 and a film 13 for forming a protective film provided on one surface (in this specification, this may be referred to as a "first surface") 10a of the support sheet 10.
The support sheet 10 includes a base material 11 and an adhesive layer 12 provided on one surface 11a of the base material 11. In the composite sheet 101 for forming a protective film, the adhesive layer 12 is disposed between the base material 11 and the film 13 for forming a protective film.
That is, the composite sheet 101 for forming a protective film is configured by sequentially laminating the base material 11, the adhesive layer 12, and the film 13 for forming a protective film in the thickness direction thereof.
The surface (in this specification, this may be referred to as "first surface") 10a of the support sheet 10 on the side of the protective film-forming film 13 is the same as the surface (in this specification, this may be referred to as "first surface") 12a of the adhesive layer 12 on the side opposite to the substrate 11.
The composite sheet 101 for forming a protective film further includes a pressure-sensitive adhesive layer 16 for a jig and a release film 15 on the film 13 for forming a protective film.
In the composite sheet 101 for forming a protective film, the film 13 for forming a protective film is laminated over the entire or almost the entire first surface 12a of the adhesive agent layer 12, and the adhesive layer 16 for a jig is laminated on a part of the surface (in this specification, this is sometimes referred to as "first surface") 13a of the film 13 for forming a protective film, which is opposite to the adhesive agent layer 12 side, that is, a region near the peripheral edge portion. Further, a release film 15 is laminated on a region of the first surface 13a of the protective film forming film 13 where the pressure-sensitive adhesive layer 16 for a jig is not laminated and a surface (which may be referred to as a "first surface" in this specification) 16a of the pressure-sensitive adhesive layer 16 opposite to the protective film forming film 13 side.
Not only in the case of the composite sheet 101 for forming a protective film, but also in the composite sheet for forming a protective film of the present embodiment, a release film (for example, the release film 15 shown in fig. 1) may have any configuration.
In the composite sheet 101 for forming a protective film, a part of a void may be generated between the release film 15 and a layer directly contacting the release film 15.
For example, although the release film 15 is shown in a state of being in contact with (laminated on) the side surface 16c of the pressure-sensitive adhesive layer 16 for a jig, the side surface 16c may not be in contact with the release film 15. Here, although the release film 15 is shown in a state of being in contact with (laminated on) the region near the jig pressure-sensitive adhesive layer 16 on the first surface 13a of the protective film forming film 13, the region may not be in contact with the release film 15.
Further, the boundary between the first surface 16a and the side surface 16c of the pressure-sensitive adhesive layer 16 for a jig may not be clearly distinguished.
The above points are also the same in the composite sheet for forming a protective film of the other embodiment provided with the pressure-sensitive adhesive layer for a jig.
The jig adhesive layer 16 is used to fix the composite sheet 101 for forming a protective film to a jig such as a ring frame.
The pressure-sensitive adhesive layer 16 for a jig may have, for example, a single-layer structure containing a pressure-sensitive adhesive component, or a multi-layer structure in which layers containing a pressure-sensitive adhesive component are laminated on both surfaces of a sheet as a core material.
In the composite sheet 101 for forming a protective film, the transmittance of light (365nm) of the support sheet 10 is preferably 40% or more.
The composite sheet 101 for forming a protective film is used in the following manner: in the state where the release film 15 is removed, any one of the work pieces (not shown) is stuck to the first surface 13a of the protective film forming film 13, and the first surface 16a of the jig adhesive layer 16 is further stuck to a jig such as a ring frame.
Fig. 2 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
In the drawings subsequent to fig. 2, the same components as those shown in the already-described drawings are denoted by the same reference numerals as those in the already-described drawings, and detailed description thereof will be omitted.
The composite sheet 102 for forming a protective film shown here is the same as the composite sheet 101 for forming a protective film shown in fig. 1, except that the shape and size of the film for forming a protective film are different, and the adhesive layer for a jig is laminated on the first surface of the adhesive layer instead of the first surface of the film for forming a protective film.
More specifically, in the composite sheet for forming a protective film 102, the film for forming a protective film 23 is laminated on a region of a part of the first surface 12a of the adhesive agent layer 12, that is, a region on the center side in the width direction (the left-right direction in fig. 2) of the adhesive agent layer 12. Further, the jig adhesive layer 16 is laminated on a region of the first surface 12a of the adhesive agent layer 12 where the protective film forming film 23 is not laminated, that is, a region near the peripheral edge portion. The release film 15 is laminated on a surface (in this specification, this is sometimes referred to as a "first surface") 23a of the protective film forming film 23 opposite to the adhesive layer 12 side and a first surface 16a of the jig adhesive layer 16.
Fig. 3 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
The composite sheet 103 for forming a protective film shown here is the same as the composite sheet 101 for forming a protective film shown in fig. 1, except that the support sheet 20 is provided instead of the support sheet 10, and the pressure-sensitive adhesive layer 16 for a jig is not provided.
The support sheet 20 is configured to include a base material 11, an adhesive agent layer 12 provided on a first surface 11a of the base material 11, and an intermediate layer 17 provided on a first surface 12a of the adhesive agent layer 12. In the composite sheet 103 for forming a protective film, the intermediate layer 17 is disposed between the adhesive layer 12 and the film 23 for forming a protective film.
That is, the composite sheet 103 for forming a protective film is formed by sequentially laminating the substrate 11, the adhesive layer 12, the intermediate layer 17, and the film 23 for forming a protective film in the thickness direction thereof.
The surface (in this specification, this may be referred to as "first surface") 20a of the support sheet 20 on the side of the protective film-forming film 23 is the same as the first surface 12a of the adhesive layer 12.
The surface (in this specification, this is sometimes referred to as "first surface") 17a of the intermediate layer 17 on the side opposite to the adhesive layer 12 is smaller in area than the first surface 12a of the adhesive layer 12 (that is, the total area of the region where the protective film forming film 23 is to be laminated and the region where the protective film forming film 23 is not to be laminated).
The planar shape of the first surface 17a of the intermediate layer 17 is not particularly limited, and may be, for example, a circular shape.
The shape and size of the first surface 17a of the intermediate layer 17 may be the same as or different from those of the first surface 23a of the protective film-forming film 23. However, the entire surface 23b of the protective film-forming film 23 opposite to the first surface 23a (which may be referred to as "second surface" in this specification) is preferably covered with the intermediate layer 17.
Fig. 4 is a cross-sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
The composite sheet 104 for forming a protective film shown here is the same as the composite sheet 101 for forming a protective film shown in fig. 1, except that the support sheet 30 is provided instead of the support sheet 10.
The support sheet 30 is formed only of the base material 11.
That is, the composite sheet 104 for forming a protective film is formed by laminating the substrate 11 and the film 13 for forming a protective film in the thickness direction thereof.
The surface (in this specification, this may be referred to as "first surface") 30a of the support sheet 30 on the side of the protective film forming film 13 is the same as the first surface 11a of the base material 11.
The substrate 11 has adhesiveness at least on the first surface 11a thereof.
The composite sheet for forming a protective film according to the present embodiment is not limited to the composite sheet for forming a protective film shown in fig. 1 to 4, and may be a composite sheet for forming a protective film obtained by modifying or deleting a part of the configuration of the composite sheet for forming a protective film shown in fig. 1 to 4, or a composite sheet for forming a protective film obtained by further adding another configuration to the composite sheet for forming a protective film described so far, as long as the effects of the present invention are not impaired. More specifically, as described below.
Although only the composite sheet 104 for forming a protective film shown in fig. 4 has been shown as the composite sheet for forming a protective film having the support sheet composed of only the base material, an example of the composite sheet for forming a protective film having the support sheet composed of only the base material is a composite sheet for forming a protective film having no adhesive layer 12 in the composite sheet 102 for forming a protective film shown in fig. 2. However, this is merely an example of another composite sheet for forming a protective film, which is provided with a support sheet composed of only a base material.
Although only the composite sheet 103 for forming a protective film shown in fig. 3 has been shown as the composite sheet for forming a protective film having an intermediate layer as a part of the support sheet, examples of the composite sheet for forming a protective film having an intermediate layer include the following composite sheets for forming a protective film. However, these composite sheets for forming a protective film are merely examples of other composite sheets for forming a protective film provided with an intermediate layer.
In the composite sheet 101 for forming a protective film shown in fig. 1, an intermediate layer similar to the intermediate layer shown in fig. 3 is provided between the adhesive layer 12 and the film 13 for forming a protective film.
The composite sheet 102 for forming a protective film shown in fig. 2 includes the same intermediate layer as the intermediate layer shown in fig. 3 between the adhesive layer 12 and the film 23 for forming a protective film.
The composite sheet 104 for forming a protective film shown in fig. 4 includes the same intermediate layer as the intermediate layer shown in fig. 3 between the base material 11 and the film 13 for forming a protective film.
Although the composite sheet for forming a protective film having a pressure-sensitive adhesive layer for a jig has been described so far, the composite sheet 101 for forming a protective film shown in fig. 1, the composite sheet 102 for forming a protective film shown in fig. 2, and the composite sheet 104 for forming a protective film shown in fig. 4 are illustrated, examples of the composite sheet for forming a protective film having a pressure-sensitive adhesive layer for a jig include a composite sheet 103 for forming a protective film shown in fig. 3, in which a pressure-sensitive adhesive layer for a jig similar to that shown in fig. 1 and the like is provided on a region where the intermediate layer 17 and the film 23 for forming a protective film are not laminated in the first surface 12a of the pressure-sensitive adhesive layer 12. However, these composite sheets for forming a protective film are merely examples of other composite sheets for forming a protective film provided with a pressure-sensitive adhesive layer for a jig.
The composite sheet for forming a protective film provided with the pressure-sensitive adhesive layer for a jig is used in such a manner that the first surface of the pressure-sensitive adhesive layer for a jig such as a ring frame is attached to the jig as in the composite sheet 101 for forming a protective film shown in fig. 1.
As described above, the composite sheet for forming a protective film of the present embodiment can be provided with a pressure-sensitive adhesive layer for a jig regardless of the form of the support sheet and the film for forming a protective film.
Although only the composite sheet 103 for forming a protective film shown in fig. 3 has been shown as the composite sheet for forming a protective film without a pressure-sensitive adhesive layer for a jig, an example of the composite sheet for forming a protective film without a pressure-sensitive adhesive layer for a jig 102 shown in fig. 2 is a composite sheet for forming a protective film without a pressure-sensitive adhesive layer 16 for a protective film. However, this composite sheet for forming a protective film is merely an example of another composite sheet for forming a protective film which does not have a pressure-sensitive adhesive layer for a jig.
In fig. 1 to 4, the base material, the adhesive agent layer, the intermediate layer, the protective film-forming film, and the release film are shown as the layers constituting the protective film-forming composite sheet, but the protective film-forming composite sheet of the present embodiment may include the other layers not belonging to any of the above layers.
When the composite sheet for forming a protective film shown in fig. 1 to 4 includes the other layer, the arrangement position thereof is not particularly limited.
In the composite sheet for forming a protective film of the present embodiment, the size and shape of each layer can be arbitrarily selected according to the purpose.
The structure of the composite sheet for forming a protective film will be described in detail below.
O support chip
The support sheet according to one embodiment of the present invention can be laminated with a protective film-forming film to form a protective film-forming composite sheet, for example, as described below.
The support sheet of the present embodiment can be used for fixing a workpiece provided with a film for forming a protective film or a cured product thereof at an arbitrary position, which will be described later.
Examples of the workpiece include a semiconductor wafer and a semiconductor device panel. A semiconductor device panel is used in a process of manufacturing a semiconductor device, and a specific example thereof is a semiconductor device panel in which a plurality of electronic components are mounted on 1 circuit board.
In the present specification, an article obtained by machining a workpiece is referred to as a "workpiece machined article". For example, when the workpiece is a semiconductor wafer, the workpiece processing object may be a semiconductor chip.
For example, when the workpiece is a semiconductor wafer, the support sheet of the present embodiment can be used for fixing a semiconductor wafer having a film for forming a protective film or a cured product thereof on the back surface.
Examples of the support sheet include: a support sheet comprising a base material and an adhesive layer provided on one surface of the base material; a support sheet composed of only a base material; a support sheet including a base, an adhesive layer provided on one surface of the base, and an intermediate layer provided on a surface of the adhesive layer opposite to the base; the support sheet is provided with a base material and an intermediate layer provided on one surface of the base material. When the support sheet includes an adhesive layer, in the protective film-forming composite sheet described later, the adhesive layer is disposed between the base material and the protective film-forming film.
When a support sheet including a base material and an adhesive layer is used, the adhesion or adhesiveness between the support sheet and the film for forming a protective film can be easily adjusted in the composite sheet for forming a protective film.
When a support sheet composed only of a base material is used, a composite sheet for forming a protective film can be manufactured at low cost.
When a support sheet including a base material, an adhesive layer, and an intermediate layer is used, a new function can be imparted to the support sheet or the composite sheet for forming a protective film. In addition, the adhesive strength or adhesiveness between the support sheet and the film for forming a protective film can be more easily adjusted than in the case of the adhesive agent layer.
The transmittance of light having a wavelength of 365nm of the support sheet is preferably 40% or more, and may be, for example, any one of 50% or more, 60% or more, and 70% or more. When the transmittance of the support sheet is not lower than the lower limit value, the illumination intensity is 5mW/cm even when the energy ray-curable adhesive is cured2Light quantity 100mJ/cm2Under the conditions (hereinafter, this may be abbreviated as "low-illuminance UV irradiation conditions"), even when light having a wavelength of 365nm is irradiated with ultraviolet light, the ultraviolet light can sufficiently reach the energy ray-curable adhesive, and the adhesive force between the protective film-forming film and the supporting sheet can be more easily reduced to less than 370mN/25 mm.
The upper limit of the transmittance of light (365nm) of the support sheet is not particularly limited, and may be, for example, 100%. For example, the support sheet having the transmittance of 97% or less can be manufactured more easily.
The transmittance of light (365nm) of the support sheet can be appropriately adjusted within a range set by arbitrarily combining any one of the lower limit values and the upper limit value described above. For example, in one embodiment, the transmittance of the support sheet is preferably 40 to 97%, more preferably 50 to 97%, and may be, for example, 60 to 97% or 70 to 97%. However, these ranges are only one example of the transmittance of the support sheet.
Base material of very good
The substrate is sheet-shaped or film-shaped, and the transmittance of light (365nm) is preferably 40% or more, and may be, for example, any one of 50% or more, 60% or more, and 70% or more.
Examples of the constituent material of the substrate include various resins.
Examples of the resin include polyolefins such as Low Density Polyethylene (LDPE) and polypropylene (PP); ethylene-methacrylic acid copolymer (EMAA); polyvinyl chloride (PVC); polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); polyether sulfone, polyacrylate; polycarbonate (PC), and the like.
The resin constituting the base material may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The substrate may be composed of 1 layer (single layer) or a plurality of layers of 2 or more, and when composed of a plurality of layers, these plurality of layers may be the same or different from each other, and the combination of these plurality of layers is not particularly limited.
In the present specification, the phrase "a plurality of layers may be the same or different from each other" means "all layers may be the same or different from each other, or only a part of layers may be the same" and "a plurality of layers are different from each other" means "at least one of the constituent materials and the thicknesses of the layers are different from each other" in the case of not limited to the base material.
The thickness of the base material is preferably 50 to 300 μm, more preferably 60 to 140 μm, and particularly preferably 80 to 100 μm. By setting the thickness of the base material to the above range, the flexibility of the composite sheet for forming a protective film and the adhesiveness to a workpiece or a workpiece are further improved.
The "thickness of the substrate" refers to the thickness of the entire substrate, and for example, the thickness of the substrate composed of a plurality of layers refers to the total thickness of all the layers constituting the substrate.
The substrate is preferably a substrate having high thickness accuracy, that is, a substrate in which unevenness in thickness is suppressed at any portion. Among the above-mentioned constituent materials, examples of the material that can be used for constituting the above-mentioned base material with high thickness accuracy include polyolefin, polyethylene terephthalate, and the like.
The base material may contain various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent materials such as the resin. For example, the transmittance of light (365nm) of the substrate can be easily adjusted by adjusting whether the substrate contains a filler or a colorant, or by adjusting the content of these components when the substrate contains a filler or a colorant.
The substrate may have adhesiveness on at least one surface by containing a component (e.g., a resin or the like) in a specific range.
As for the optical characteristics of the base material, the support sheet preferably satisfies the previously described condition of transmittance of light (365 nm).
For example, as described above, since the support sheet may be composed of only the base material, the transmittance of light (365nm) of the base material is the same as that of light (365nm) of the support sheet described above.
Further, the transmittance of the light (365nm) of the base material may be, for example, 40% or more, 50% or more, 60% or more, or 70% or more for the same reason as the transmittance of the light (365nm) of the support sheet.
The upper limit of the transmittance of the base material for light (365nm) is not particularly limited, and may be, for example, 100% for the same reason as the transmittance of the support sheet for light (365 nm). For example, the substrate having a transmittance of 97% or less can be manufactured or obtained more easily.
The transmittance of light (365nm) of the base material can be appropriately adjusted within a range set by arbitrarily combining any of the lower limit values and the upper limit value described above. For example, in one embodiment, the transmittance of the substrate may be in any range of 40 to 97%, 50 to 97%, 60 to 97%, and 70 to 97%. However, these ranges are only one example of the transmittance of the substrate.
In order to improve the adhesion between the substrate and a layer (e.g., an adhesive layer, a film for forming a protective film, etc.) provided on the substrate, the surface may be subjected to a sandblasting treatment, a roughening treatment by a solvent treatment, etc.; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and other oxidation treatments. In addition, the surface of the substrate may be subjected to primer treatment.
Furthermore, the substrate may have the following layers: an antistatic coating layer; and a layer for preventing adhesion of the substrate to another sheet or adhesion of the substrate to the adsorption stage when the composite sheet for forming a protective film is stacked and stored.
The substrate can be manufactured by a known method. For example, a resin-containing substrate can be produced by molding a resin composition containing the resin.
Adhesive layer
The adhesive layer is a sheet or film, and the protective film-forming film or a cured product thereof preferably has an adhesive force of less than 370mN/25mm, more preferably less than 250mN/25m m, and particularly preferably less than 200mN/25mm, with the supporting sheet.
When the adhesion between the protective film-forming film or the cured product thereof and the support sheet is less than the upper limit value, the semiconductor chip can be easily picked up from the support sheet without damaging the semiconductor chip when the semiconductor chip is picked up from the support sheet.
In particular, when the adhesive contained in the adhesive layer is an energy ray-curable adhesive, the adhesive strength between the energy ray cured product obtained by ultraviolet irradiation under the low-illuminance UV irradiation condition and the support sheet is made smaller than the upper limit value, whereby the risk of the semiconductor chip being irradiated with ultraviolet light can be reduced, and the semiconductor chip can be easily picked up from the support sheet without damaging the semiconductor chip when the semiconductor chip is picked up from the support sheet.
The lower limit of the adhesive force between the protective film-forming film or the cured product thereof and the supporting sheet may be 50mN/25mm or more. If the adhesion is not less than the lower limit, it is possible to prevent the adjacent semiconductor chips from colliding with each other and being damaged when the semiconductor chips are conveyed.
The adhesive layer contains an adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferred.
In addition, in the present specification, the "adhesive resin" includes a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only a resin having self-adhesiveness but also a resin exhibiting adhesiveness by being used together with other components such as an additive, a resin exhibiting adhesiveness due to the presence of a trigger (trigger) such as heat or water, and the like.
The adhesive layer may be composed of 1 layer (single layer) or a plurality of layers of 2 or more, and in the case of being composed of a plurality of layers, these plurality of layers may be the same or different from each other, and the combination of these plurality of layers is not particularly limited.
The thickness of the adhesive layer is preferably 1 to 14 μm, more preferably 2 to 12 μm, and for example, may be 3 to 8 μm. By setting the thickness of the adhesive agent layer to be equal to or greater than the lower limit value, the effect of providing the adhesive agent layer can be more remarkably obtained. When the thickness of the adhesive layer is not more than the upper limit, printing can be performed more favorably on the protective film-forming film or the cured product thereof in the protective film-forming composite sheet. Further, the print can be recognized more favorably from the outside of the protective film forming composite sheet on the support sheet side through the support sheet.
The "thickness of the adhesive agent layer" refers to the thickness of the entire adhesive agent layer, and for example, the thickness of the adhesive agent layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive agent layer.
The adhesive layer may be formed using an energy ray-curable adhesive, or may be formed using a non-energy ray-curable adhesive. That is, the adhesive layer may be either energy ray-curable or non-energy ray-curable. The energy ray-curable adhesive agent layer can be easily adjusted in physical properties before and after curing. For example, before picking up a semiconductor chip with a protective film or a semiconductor chip with a film for forming a protective film described later, these semiconductor chips can be picked up more easily by curing an energy ray-curable adhesive layer.
In the present specification, the "energy ray" refers to a ray having an energy quantum in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, radiation, an electron beam, and the like. For example, the ultraviolet rays may be irradiated by using a high-pressure mercury lamp, a fusion H lamp (fusion H lamp), a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray-curable property" refers to a property of curing by irradiation with an energy ray, and "non-energy ray-curable property" refers to a property of not curing even by irradiation with an energy ray.
Adhesive composition
The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive layer can be formed at a target site by applying an adhesive composition to a surface to be formed of the adhesive layer and drying the composition as necessary. The content ratio of the components that do not vaporize at ordinary temperature in the adhesive composition is generally the same as the content ratio of the components in the adhesive layer. In the present specification, "normal temperature" means a temperature at which cooling or heating is not particularly performed, that is, a normal temperature, and includes, for example, a temperature of 15 to 25 ℃.
The application of the adhesive composition may be carried out by a known method, and examples thereof include methods using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described later, it is preferably dried by heating. The adhesive composition containing a solvent is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes, for example.
When the adhesive layer is provided on the substrate, for example, the adhesive composition may be applied to the substrate and dried as necessary, thereby laminating the adhesive layer on the substrate. In addition, when the adhesive layer is provided on the substrate, for example, the adhesive layer may be laminated on the substrate by applying an adhesive composition on a release film, drying the adhesive composition as needed, thereby forming the adhesive layer on the release film and bonding an exposed surface of the adhesive layer to one surface of the substrate. The release film in this case may be removed at any time during the production process or the use process of the composite sheet for forming a protective film.
When the adhesive layer is energy ray-curable, examples of the energy ray-curable adhesive composition include: an adhesive composition (I-1) comprising a non-energy-ray-curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as "adhesive resin (I-1 a)") and an energy-ray-curable compound; an adhesive composition (I-2) comprising an energy ray-curable adhesive resin (I-2a) having an unsaturated group introduced into a side chain of the adhesive resin (I-1a) (hereinafter, this may be abbreviated as "adhesive resin (I-2 a)"); and an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound.
When the adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable adhesive composition include the adhesive composition (I-4) containing the adhesive resin (I-1 a).
[ adhesive resin (I-1a) ]
The adhesive resin (I-1a) of the adhesive composition (I-1), the adhesive composition (I-2), the adhesive composition (I-3) and the adhesive composition (I-4) (hereinafter, these adhesive compositions are collectively abbreviated as "adhesive compositions (I-1) to (I-4)") is preferably an acrylic resin.
Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate.
Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched.
In the present specification, "(meth) acrylic acid" is a concept including "acrylic acid" and "methacrylic acid". The same applies to terms similar to those of (meth) acrylic acid, for example, "(meth) acryloyl" means a concept including "acryloyl" and "methacryloyl", and "(meth) acrylate" means a concept including "acrylate" and "methacrylate".
The acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate.
Examples of the functional group-containing monomer include a functional group-containing monomer which can introduce an unsaturated group into a side chain of an acrylic polymer by reacting the functional group with a crosslinking agent described later to become a starting point of crosslinking or reacting the functional group with an unsaturated group in an unsaturated group-containing compound described later.
Examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
The acrylic polymer may further have a structural unit derived from other monomer in addition to a structural unit derived from an alkyl (meth) acrylate and a structural unit derived from a functional group-containing monomer.
The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth) acrylate or the like.
Examples of the other monomer include styrene, α -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.
In the adhesive compositions (I-1) to (I-4), the acrylic resin such as the acrylic polymer may have only one type of structural unit, or two or more types of structural units, and when two or more types of structural units are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass based on the total amount of the structural units.
The adhesive resin (I-1a) contained in the adhesive composition (I-1) or the adhesive composition (I-4) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1) or the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass relative to the total mass of the adhesive composition (I-1) or the adhesive composition (I-4).
[ adhesive resin (I-2a) ]
The adhesive resin (I-2a) in the adhesive compositions (I-2) and (I-3) can be obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group.
The unsaturated group-containing compound has a group capable of bonding to the adhesive resin (I-1a) by further reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray-polymerizable unsaturated group.
Examples of the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (ethylene group), and an allyl group (2-propenyl group), and a (meth) acryloyl group is preferable.
Examples of the group capable of bonding to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group capable of bonding to a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding to a carboxyl group or an epoxy group.
Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate.
The adhesive resin (I-2a) contained in the adhesive composition (I-2) or (I-3) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2) or (I-3), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass based on the total mass of the adhesive composition (I-2) or (I-3).
[ energy ray-curable Compound ]
Examples of the energy ray-curable compound in the adhesive compositions (I-1) and (I-3) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray.
In order to reduce the influence of irradiation with energy rays on the semiconductor chip, the energy ray-curable compound is preferably a compound which cures even when irradiated with ultraviolet rays under low-illuminance UV irradiation conditions and has an adhesion between the obtained energy ray-cured product and the support sheet of less than 370mN/25 mm. The low-illuminance UV irradiation condition is the condition.
Examples of the monomer in the energy ray-curable compound include polyvalent (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates, and the like.
The energy ray-curable compound may be an oligomer obtained by polymerizing the above-mentioned monomers, for example.
The energy ray-curable compound contained in the adhesive composition (I-1) or (I-3) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass relative to the total mass of the adhesive composition (I-1).
In the adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ crosslinking agent ]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), the adhesive composition (I-1) or (I-4) preferably further contains a crosslinking agent.
Further, for example, when the acrylic polymer having the same structural unit as that derived from the functional group-containing monomer in the adhesive resin (I-1a) is used as the adhesive resin (I-2a), the adhesive composition (I-2) or (I-3) may further contain a crosslinking agent.
The crosslinking agent reacts with the functional groups, for example, to crosslink the adhesive resins (I-1a) with each other or the adhesive resins (I-2a) with each other.
Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine crosslinking agents (crosslinking agents having an aziridinyl group) such as Hexa [1- (2-methyl) -azidinyl ] triphosphotriazine (Hexa [1- (2-methyl) -azidinyl ] triphosphatriazine); metal chelate crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelates; an isocyanurate-based crosslinking agent (a crosslinking agent having an isocyanurate skeleton), and the like.
The crosslinking agent contained in the adhesive composition (I-1), (I-2) or (I-4) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1) or (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, and may be, for example, any one of 0.01 to 35 parts by mass and 0.01 to 20 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-1 a).
In the adhesive composition (I-2) or (I-3), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, and may be, for example, any one of 0.01 to 35 parts by mass, 0.01 to 20 parts by mass, and 0.01 to 10 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ photopolymerization initiator ]
The adhesive compositions (I-1), (I-2) and (I-3) (hereinafter, these adhesive compositions are collectively abbreviated as "adhesive compositions (I-1) to (I-3)") may further contain a photopolymerization initiator. The adhesive compositions (I-1) to (I-3) containing a photopolymerization initiator have a sufficient curing reaction even when irradiated with a relatively low energy ray such as ultraviolet ray.
Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-dimethoxy-1, 2-diphenylethan-1-one, and 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfur compounds such as benzylphenylsulfide, tetramethylthiuram monosulfide and the like; α -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxy compound; diketone compounds such as diacetyl; benzil (benzil); dibenzoyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
As the photopolymerization initiator, for example, a photosensitizer such as amine can be used.
The photopolymerization initiators contained in the adhesive compositions (I-1) to (I-3) may be only one type, or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the energy ray-curable compound. The content of the photopolymerization initiator in the adhesive composition (I-2) is preferably 0.01 to 20 parts by mass, and may be, for example, any one of 0.01 to 10 parts by mass and 0.01 to 5 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-2 a).
In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound.
[ other additives ]
The adhesive compositions (I-1) to (I-4) may contain other additives not belonging to any of the above components within a range not impairing the effects of the present invention.
Examples of the other additives include known additives such as antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments and dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts).
The reaction retarder is an additive that suppresses unintended crosslinking reactions in the adhesive compositions (I-1) to (I-4) during storage, for example, by the action of a catalyst mixed in the adhesive compositions (I-1) to (I-4). Examples of the reaction retarder include a reaction retarder which forms a chelate complex (chelate complex) by using a chelate of a catalyst, and more specifically, a reaction retarder having two or more carbonyl groups (-C (═ O) -) in one molecule.
The other additives contained in the adhesive compositions (I-1) to (I-4) may be only one type, or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
The content of the other additives in the adhesive compositions (I-1) to (I-4) is not particularly limited, and may be appropriately selected depending on the kind thereof.
[ solvent ]
The adhesive compositions (I-1) to (I-4) may contain a solvent, and the suitability for surface coating to be coated is improved by containing a solvent in the adhesive compositions (I-1) to (I-4).
In the present specification, unless otherwise specified, the concept of "solvent" includes not only a solvent that dissolves a target component but also a dispersion medium that disperses the target component.
The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.
The adhesive compositions (I-1) to (I-4) may contain only one solvent, or may contain two or more solvents, and when two or more solvents are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the solvent in the adhesive compositions (I-1) to (I-4) is not particularly limited, and may be appropriately adjusted.
Preparation method of adhesive composition
The adhesive compositions such as the adhesive compositions (I-1) to (I-4) can be obtained by blending the adhesive and components for constituting the adhesive composition according to need, such as components other than the adhesive.
The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.
In the blending, the method for mixing the components is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.
The temperature and time for adding and mixing the components are not particularly limited and may be appropriately adjusted as long as the components are not deteriorated, but the temperature is preferably 15 to 30 ℃.
Middle layer very high
The intermediate layer is sheet-shaped or film-shaped, and has a light transmittance (365nm) of preferably 40% or more, and may be, for example, 50% or more, 60% or more, or 70% or more.
In the composite sheet for forming a protective film, the intermediate layer is disposed between the adhesive layer and the film for forming a protective film.
The kind of the intermediate layer may be arbitrarily selected according to the purpose, and is not particularly limited.
The optical properties of the intermediate layer are preferably such that the support sheet satisfies the above-described conditions for the transmittance of light (365 nm).
The intermediate layer can be formed by a known method according to the kind thereof. For example, the intermediate layer containing a resin as a main component can be formed by molding a resin composition containing the resin.
The intermediate layer may be, for example, a release property improving layer having one surface thereof subjected to a release treatment.
Peeling Performance improving layer
Examples of the peelability improving layer include a peelability improving layer composed of a plurality of layers including a resin layer and a release treatment layer formed on the resin layer.
In the composite sheet for forming a protective film, the peeling property improving layer is disposed so that the peeling treatment layer faces the protective film forming film side.
The resin layer in the releasability-improving layer can be produced by molding a resin composition containing a resin.
The releasability-improving layer can be produced by subjecting one surface of the resin layer to a release treatment.
The resin layer can be peeled off using various known release agents such as alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and paraffin.
The release agent is preferably an alkyd type, silicone or fluorine type release agent in view of heat resistance.
The resin as a constituent material of the resin layer is not particularly limited as long as it is appropriately selected according to the purpose.
Examples of preferable resins include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), Polyethylene (PE), and polypropylene (PP).
The resin layer may be composed of 1 layer (single layer) or a plurality of layers of 2 or more, and when composed of a plurality of layers, these plurality of layers may be the same or different from each other, and the combination of these plurality of layers is not particularly limited.
The thickness of the release property improving layer (the total thickness of the resin layer and the release treatment layer) is preferably 10 to 2000nm, more preferably 25 to 1500nm, and particularly preferably 50 to 1200 nm. When the thickness of the peelability improvement layer is equal to or greater than the lower limit value, the effect of the peelability improvement layer becomes more remarkable, and the effect of suppressing breakage such as cutting of the peelability improvement layer becomes higher. By setting the thickness of the peeling property improving layer to the upper limit or less, a semiconductor chip provided with a protective film or a film for forming a protective film, which will be described later, on the back surface can be picked up more easily.
Protective film formation film
The protective film-forming film of the present embodiment can be laminated on a support sheet to form a protective film-forming composite sheet, for example, as described later.
The protective film-forming film forms a protective film for protecting a workpiece and an arbitrary position of a workpiece. When the workpiece is a semiconductor wafer, by using the film for forming a protective film of the present embodiment, a protective film can be formed on the surface of the semiconductor wafer or the semiconductor chip opposite to the circuit formation surface (in this specification, both of them are sometimes referred to as "back surface"). In the present specification, the workpiece with the protective film may be referred to as a "workpiece with a protective film", and the semiconductor chip with a protective film on the back surface may be referred to as a "semiconductor chip with a protective film".
The film for forming a protective film is soft and can be easily attached to an object to be attached such as a workpiece or a workpiece.
The film for forming a protective film may be cured to function as a protective film, or may be uncured to function as a protective film. The protective film-forming film that functions as a protective film in an uncured state can be regarded as a protective film formed, for example, at the stage of being stuck to a target position of a workpiece.
The protective film has a light (365nm) transmittance of 0.3% or less. Even when ultraviolet rays are irradiated, the semiconductor chip can be prevented from being damaged or malfunctioning. In particular, even when the adhesive is an energy ray-curable adhesive and ultraviolet rays are irradiated to cure the adhesive, the semiconductor chip can be prevented from being broken or malfunctioning.
The protective film-forming film and the cured product thereof (i.e., the protective film) exhibit substantially the same transmittance with respect to light having the same wavelength.
The transmittance of light (365nm) of the protective film-forming film may be, for example, any one of 0.3% or less, 0.25% or less, 0.2% or less, 0.15% or less, 0.1% or less, and 0.05%. By setting the transmittance of the protective film forming film to the upper limit or less, it is possible to suppress the semiconductor chip from being broken or malfunctioning even when ultraviolet rays are irradiated.
The lower limit of the transmittance of the protective film-forming film to light (365nm) is not particularly limited, and may be 0%, for example. For example, the protective film having a transmittance of 0% or more can be easily produced.
The transmittance of light (365nm) of the protective film forming film can be appropriately adjusted within a range set by arbitrarily combining the lower limit value and an arbitrary upper limit value. For example, in one embodiment, the transmittance of the protective film forming film is preferably 0 to 0.3%, and may be, for example, any one of 0 to 0.25%, 0 to 0.2%, 0 to 0.15%, 0 to 0.1%, and 0 to 0.05%. However, these ranges are only one example of the transmittance of the protective film forming film.
As described above, the protective film-forming film may be curable or non-curable.
The curable protective film-forming film may be either thermosetting or energy ray-curable, or may have both thermosetting and energy ray-curable properties, but is preferably thermosetting or non-curable in order to reduce the risk of irradiation of a workpiece with an energy ray.
In the present specification, "non-curable" refers to a property that does not cure even by any means such as heating or irradiation with an energy ray.
When the protective film is formed by thermally curing the protective film-forming film, the protective film can be formed with high protective performance even if the protective film-forming film is thick because the protective film is sufficiently cured by heating, unlike the case of curing by irradiation with an energy ray. Further, by using a common heating means such as a heating oven, a large number of protective film forming films can be collectively heated and thermally cured.
When the protective film is formed by curing the protective film-forming film by irradiation with an energy ray, the protective film-forming composite sheet does not need to have heat resistance unlike the case of heat curing, and a wide range of protective film-forming composite sheets can be configured. Further, the curing can be performed in a short time by irradiation with energy rays.
When the protective film-forming film is used as a protective film without curing, the curing step can be omitted, and therefore a work with a protective film can be produced in a simplified step.
The protective film-forming film may be composed of 1 layer (single layer) or a plurality of 2 or more layers regardless of whether the protective film-forming film is curable or non-curable, and when it is curable, the protective film-forming film may be composed of 1 layer (single layer) or a plurality of 2 or more layers regardless of whether it is thermosetting or energy ray-curable. When the laminate is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 80 μm, particularly preferably 5 to 60 μm, and may be in any range of 5 to 40 μm and 5 to 20 μm, regardless of the thermosetting property or energy ray-curable property, and when it is curable, the thickness of the protective film-forming film is preferably 1 to 100 μm, more preferably 3 to 80 μm, particularly preferably 5 to 60 μm, and may be in any range of 5 to 40 μm and 5 to 20 μm, for example. When the thickness of the protective film forming film is not less than the lower limit value, a protective film having higher protective performance can be formed. When the thickness of the protective film-forming film is not more than the upper limit, an excessively large thickness can be avoided.
The "thickness of the protective film-forming film" refers to the thickness of the entire protective film-forming film, and for example, the thickness of the protective film-forming film composed of a plurality of layers refers to the total thickness of all the layers constituting the protective film-forming film.
The protective film-forming film preferably has a transmittance of light having a wavelength of 555nm (hereinafter, this may be abbreviated as "light (555 nm)" in the present specification) of 5% or less, more preferably 4% or less, and particularly preferably 3% or less. By setting the transmittance of light (555nm) of the protective film forming film to the upper limit or less, grinding marks on the back surface of the wafer and laser printing for process control can be suppressed from being visually recognized, the design is excellent, and the possibility of causing a reading failure of the laser printing on the surface of the protective film is reduced.
The protective film-forming film preferably has a transmittance of light having a wavelength of 800nm (hereinafter, this may be abbreviated as "light (800 nm)" in the present specification) of less than 20%, more preferably less than 17%. Particularly preferably less than 15%. When the transmittance of light (800nm) of the film for forming a protective film is less than the upper limit value, grinding marks on the back surface of the wafer and laser printing for process control can be further suppressed from being visually recognized, the design is more excellent, and the possibility of causing a reading failure of the laser printing on the surface of the protective film is further reduced.
Composition for Forming protective film
The protective film-forming film can be formed using a protective film-forming composition containing the constituent material thereof. For example, the protective film-forming film can be formed by applying the protective film-forming composition to the surface to be formed, and drying the composition as needed. The ratio of the contents of the components that do not vaporize at ordinary temperature in the protective film-forming composition to each other is generally the same as the ratio of the contents of the components to each other in the protective film-forming film.
The film for forming a thermosetting protective film can be formed using the composition for forming a thermosetting protective film, the film for forming an energy ray-curable protective film can be formed using the composition for forming an energy ray-curable protective film, and the film for forming a non-curable protective film can be formed using the composition for forming a non-curable protective film. In the present specification, when the protective film-forming film has both properties of thermosetting and energy ray-curable properties, the protective film-forming film is used as a thermosetting film when the contribution of thermosetting of the protective film-forming film is larger than the contribution of energy ray-curing in forming the protective film. In contrast, when the energy ray-curable contribution of the protective film-forming film is larger than the thermosetting contribution, the protective film-forming film is used as the energy ray-curable film for the formation of the protective film.
The coating of the protective film-forming composition can be performed, for example, by the same method as the above-described coating of the adhesive composition.
The drying conditions of the protective film forming composition are not particularly limited, regardless of whether the protective film forming film is curable or non-curable, and when it is curable, the drying conditions of the protective film forming composition are not particularly limited, regardless of whether it is thermosetting or energy ray curable. However, when the protective film-forming composition contains a solvent described later, it is preferably dried by heating. The protective film-forming composition containing a solvent is preferably dried by heating at 70 to 130 ℃ for 10 seconds to 5 minutes, for example. However, it is preferable to heat-dry the thermosetting protective film-forming composition without thermally curing the thermosetting protective film-forming composition itself and the thermosetting protective film-forming film formed from the composition,
the film for forming a thermosetting protective film, the film for forming an energy ray-curable protective film, and the film for forming a non-curable protective film will be described in this order.
Film for forming very high thermosetting protective film
The curing conditions for forming the protective film by attaching the film for forming a thermosetting protective film to a target position of the workpiece and thermally curing the film are not particularly limited as long as the protective film has a curing degree of a degree sufficient to exhibit the function thereof, and may be appropriately selected depending on the kind of the film for forming a thermosetting protective film.
For example, the heating temperature for thermosetting the film for forming a thermosetting protective film is preferably 100 to 200 ℃, more preferably 110 to 180 ℃, and particularly preferably 120 to 170 ℃. The heating time during the thermal curing is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.
Examples of a preferable thermosetting protective film-forming film include a thermosetting protective film-forming film containing a polymer component (a) and a thermosetting component (B). The polymer component (a) is a component obtained by polymerization of a polymerizable compound. The thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction by using heat as reaction inducing agent. The polymerization reaction in the present specification also includes a polycondensation reaction.
< composition for Forming thermosetting protective film (III-1) >
Examples of a preferable thermosetting protective film-forming composition include a thermosetting protective film-forming composition (III-1) (which may be abbreviated as "composition (III-1)" in the present specification) containing the polymer component (A) and the thermosetting component (B).
[ Polymer component (A) ]
The polymer component (a) is a component for imparting film formability, flexibility, or the like to the thermosetting protective film.
The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
Examples of the polymer component (a) include acrylic resins, polyesters, urethane resins, acrylic urethane resins, silicone resins, rubber resins, phenoxy resins, thermosetting polyimides, and the like, and acrylic resins are preferred.
As the acrylic resin in the polymer component (a), a known acrylic polymer can be mentioned.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10000 to 2000000, more preferably 100000 to 1500000. By setting the weight average molecular weight of the acrylic resin to be not less than the lower limit, the shape stability (stability with time during storage) of the film for forming a thermosetting protective film is improved. Further, by setting the weight average molecular weight of the acrylic resin to be not more than the upper limit, the film for forming a thermosetting protective film can easily follow the uneven surface of the adherend, and generation of voids and the like between the adherend and the film for forming a thermosetting protective film can be further suppressed.
In the present specification, unless otherwise specified, "weight average molecular weight" refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.
The glass transition temperature (Tg) of the acrylic resin is preferably-60 to 70 ℃, and more preferably-30 to 50 ℃. When the Tg of the acrylic resin is not less than the lower limit, for example, the adhesion between the cured product of the protective film-forming film and the supporting sheet can be suppressed, and the releasability of the supporting sheet can be appropriately improved. Further, by setting Tg of the acrylic resin to the upper limit or less, the adhesive strength between the thermosetting protective film-forming film and the cured product thereof and the adherend is improved.
The acrylic resin has m kinds of structural units (m is an integer of 2 or more), and m kinds of monomers from which these structural units are derived are assigned in order of 1 to m, respectively, with no repetition, and when the acrylic resin is named as "monomer m", the glass transition temperature (Tg) of the acrylic resin can be calculated using the following formula Fox.
[ mathematical formula 1]
Figure BDA0002459953400000321
Wherein Tg is the glass transition temperature of the acrylic resin, m is an integer of 2 or more, Tgk is the glass transition temperature of a homopolymer of the monomer m, and W is the molecular weight of the acrylic resinkIs the mass fraction of structural units m derived from the monomer m in the acrylic resin, wherein WkSatisfies the following numerical expression.
[ mathematical formula 2]
Figure BDA0002459953400000322
In the formula, m and WkAnd m and W abovekThe same is true.
The Tgk can be expressed by the values described in the handbook of Polymer data-macromolecules データ and ハンドブック or the handbook of adhesions (adhesions ハンドブック). For example, a homopolymer of methyl acrylate has Tgk of 10 deg.C, a homopolymer of methyl methacrylate has Tgk of 105 deg.C, and a homopolymer of 2-hydroxyethyl acrylate has Tgk of-15 deg.C.
Examples of the acrylic resin include polymers of one or two or more kinds of (meth) acrylic acid esters; and copolymers of two or more monomers selected from (meth) acrylic acid, itaconic acid, ethyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.
Examples of the (meth) acrylic ester constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, n-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth, Alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is 1 to 18 carbon atoms, such as tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate);
Cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate;
(meth) acrylic acid imide;
glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate;
hydroxyl group-containing (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
and substituted amino group-containing (meth) acrylates such as N-methylaminoethyl (meth) acrylate. The "substituted amino group" refers to a group in which 1 or 2 hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.
The acrylic resin may be, for example, a resin obtained by copolymerizing one or more monomers selected from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol acrylamide, in addition to the (meth) acrylate.
The acrylic resin may be composed of only one monomer, or two or more monomers, and when two or more monomers are used, the combination and ratio thereof may be arbitrarily selected.
The acrylic resin may have a functional group capable of bonding with other compounds, such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, and isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) described later, or may be directly bonded to another compound without via the crosslinking agent (F). By bonding the acrylic resin to another compound through the functional group, the reliability of a package obtained using the composite sheet for forming a protective film tends to be improved.
In the present invention, as the polymer component (a), a thermoplastic resin other than an acrylic resin (hereinafter, it may be simply abbreviated as "thermoplastic resin") may be used alone without using an acrylic resin, or an acrylic resin and a thermoplastic resin other than an acrylic resin may be used together. By using the thermoplastic resin, the releasability of the protective film from the support sheet is improved, the thermosetting protective film-forming film can easily follow the uneven surface of the adherend, and generation of voids and the like between the adherend and the thermosetting protective film-forming film can be further suppressed.
The weight average molecular weight of the thermoplastic resin is preferably 1000 to 100000, and more preferably 3000 to 80000.
The glass transition temperature (Tg) of the thermoplastic resin is preferably-30 to 150 ℃, and more preferably-20 to 120 ℃.
Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutylene, polybutadiene, and polystyrene.
The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (III-1), the proportion of the content of the polymer component (a) relative to the total content of all components except the solvent (i.e., the proportion of the content of the polymer component (a) in the film for forming a thermosetting protective film relative to the total mass of the film for forming a thermosetting protective film) is, regardless of the type of the polymer component (a), preferably 10 to 85 mass%, more preferably 15 to 70 mass%, still more preferably 20 to 60 mass%, and for example, may be any one of 20 to 45 mass% and 20 to 35 mass%, or may be any one of 35 to 60 mass% and 45 to 60 mass%.
The polymer component (A) may be a thermosetting component (B). In the present invention, when the composition (III-1) contains the above-mentioned components belonging to both the polymer component (A) and the thermosetting component (B), the composition (III-1) is regarded as containing the polymer component (A) and the thermosetting component (B).
[ thermosetting component (B) ]
The thermosetting component (B) is a component for curing the film for forming a thermosetting protective film.
The thermosetting component (B) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Examples of the thermosetting component (B) include epoxy thermosetting resins, polyimide resins, unsaturated polyester resins, and the like, and epoxy thermosetting resins are preferable.
(epoxy thermosetting resin)
The epoxy thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2). The epoxy thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Epoxy resin (B1)
Examples of the epoxy resin (B1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated products thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, and epoxy resins having a phenylene skeleton.
As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can be used. The compatibility of the epoxy resin having an unsaturated hydrocarbon group with the acrylic resin is higher than that of the epoxy resin having no unsaturated hydrocarbon group with the acrylic resin. Therefore, the use of the epoxy resin having an unsaturated hydrocarbon group improves the reliability of a workpiece with a protective film obtained by using the composite sheet for forming a protective film.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a part of the epoxy group of the polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. The compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof to an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethylene group (vinyl group), a 2-propenyl group (allyl group), (meth) acryloyl group, and (meth) acrylamido group, with acryloyl group being preferred.
The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30000, more preferably 300 to 10000, and particularly preferably 300 to 3000, in view of curability of the thermosetting protective film-forming film and strength and heat resistance of the protective film as a cured product thereof.
The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000g/eq, more preferably 150 to 950 g/eq.
The epoxy resins (B1) may be used singly or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
Heat-curing agent (B2)
The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group obtained by anhydrizing an acid group, and the like, and a phenolic hydroxyl group, an amino group, or a group obtained by anhydrizing an acid group are preferable, and a phenolic hydroxyl group or an amino group is more preferable.
Examples of the phenol curing agent having a phenolic hydroxyl group in the heat curing agent (B2) include polyfunctional phenol resins, bisphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins.
As the amine-based curing agent having an amino group in the thermosetting agent (B2), dicyandiamide and the like can be mentioned, for example.
The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the unsaturated hydrocarbon group-containing thermosetting agent (B2) include a compound in which a part of the hydroxyl groups of the phenol resin is substituted with an unsaturated hydrocarbon group-containing group, a compound in which an unsaturated hydrocarbon group-containing group is directly bonded to an aromatic ring of the phenol resin, and the like.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.
When the heat-curing agent (B2) is used as the phenol-based curing agent, the heat-curing agent (B2) preferably has a high softening point or glass transition temperature, from the viewpoint of improving the peelability of the protective film from the support sheet.
Among the thermosetting agents (B2), for example, the number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolak-type phenol resin, a dicyclopentadiene-type phenol resin, or an aralkyl-type phenol resin is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 3000.
In the thermosetting agent (B2), the molecular weight of the non-resin component such as bisphenol or dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.
The heat-curing agent (B2) may be used alone or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
The content of the thermosetting agent (B2) in the composition (III-1) and the film for forming a thermosetting protective film is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, and may be, for example, any one of 0.5 to 25 parts by mass, 0.5 to 10 parts by mass, and 0.5 to 5 parts by mass, based on 100 parts by mass of the content of the epoxy resin (B1). By setting the content of the thermosetting agent (B2) to the lower limit or more, it becomes easier to cure the thermosetting protective film-forming film. When the content of the thermosetting agent (B2) is not more than the upper limit, the moisture absorption rate of the thermosetting protective film-forming film is reduced, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved.
In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is preferably 5 to 120 parts by mass, more preferably 5 to 80 parts by mass, and may be, for example, any one of 5 to 40 parts by mass, 5 to 20 parts by mass, and 5 to 10 parts by mass, or may be any one of 40 to 80 parts by mass, 50 to 75 parts by mass, and 60 to 75 parts by mass, relative to 100 parts by mass of the content of the polymer component (A). When the content of the thermosetting component (B) is in the above range, for example, the adhesion between the cured product of the protective film-forming film and the supporting sheet is suppressed, and the releasability of the supporting sheet is improved.
[ curing Accelerator (C) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing speed of the composition (III-1).
Examples of the preferable curing accelerator (C) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles (imidazole in which 1 or more hydrogen atoms are replaced with a group other than a hydrogen atom) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organophosphines (phosphines in which 1 or more hydrogen atoms are substituted with an organic group), such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.
The curing accelerator (C) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the curing accelerator (C) is used, the content of the curing accelerator (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, based on 100 parts by mass of the thermosetting component (B) in the composition (III-1) and the film for forming a thermosetting protective film. By setting the content of the curing accelerator (C) to the lower limit or more, the effect of using the curing accelerator (C) can be more remarkably obtained. When the content of the curing accelerator (C) is not more than the above upper limit, for example, the effect of suppressing the occurrence of segregation due to the highly polar curing accelerator (C) moving to the side of the adhesive interface with the adherend in the film for forming a thermosetting protective film under high temperature and high humidity conditions becomes high. As a result, the reliability of the workpiece with the protective film obtained by using the composite sheet for forming the protective film is further improved.
[ Filler (D) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). By incorporating the filler (D) into the thermosetting protective film-forming film, it becomes easy to adjust the thermal expansion coefficient between the thermosetting protective film-forming film and the cured product thereof (i.e., the protective film), and by optimizing the thermal expansion coefficient for the object to be protected, the reliability of the work piece with the protective film obtained by using the composite sheet for protecting film formation is further improved. Further, by incorporating the filler (D) into the thermosetting protective film-forming film, the moisture absorption rate of the protective film can be reduced, and the heat dissipation can be improved.
The filler (D) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.
Examples of preferable inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium white, 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, the inorganic filler is preferably silica or alumina, and more preferably silica.
The filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the composition (III-1), the proportion of the content of the filler (D) relative to the total content of all the components except the solvent (i.e., the proportion of the content of the filler (D) in the film for forming a thermosetting protective film relative to the total mass of the film for forming a thermosetting protective film) is preferably 15 to 70% by mass, more preferably 30 to 60% by mass, and may be, for example, any one of 35 to 60% by mass, 40 to 60% by mass, and 45 to 60% by mass, and may be any one of 30 to 55% by mass, 30 to 50% by mass, and 30 to 45% by mass. When the ratio is in the above range, it becomes easier to adjust the thermal expansion coefficient of the film for forming a thermosetting protective film and the cured product thereof.
[ coupling agent (E) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). By using a coupling agent having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (E), the adhesiveness and adhesion of the film for forming a thermosetting protective film to an adherend can be improved. Further, by using the coupling agent (E), the cured product of the thermosetting protective film-forming film has improved water resistance without impairing heat resistance.
The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group of the polymer component (a), the thermosetting component (B), or the like, and more preferably a silane coupling agent.
Examples of the preferable silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, and the like, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.
The coupling agent (E) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the film for forming a thermosetting protective film is preferably 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and particularly preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the total content of the polymer component (A) and the thermosetting component (B). When the content of the coupling agent (E) is not less than the lower limit, effects due to the use of the coupling agent (E) such as improvement in dispersibility of the filler (D) in the resin and improvement in adhesion between the thermosetting protective film-forming film and the adherend can be more remarkably obtained. Further, by setting the content of the coupling agent (E) to the upper limit value or less, the occurrence of degassing can be further suppressed.
[ crosslinking agent (F) ]
When a component having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group, which can be bonded to another compound, such as the acrylic resin, is used as the polymer component (a), the composition (III-1) and the film for forming a thermosetting protective film may contain the crosslinking agent (F). The crosslinking agent (F) is a component for bonding and crosslinking the functional group in the polymer component (a) with another compound, and the initial adhesive force and cohesive force of the film for forming a thermosetting protective film can be adjusted by crosslinking.
Examples of the crosslinking agent (F) include an organic polyisocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent (a crosslinking agent having an aziridine group), and the like.
The crosslinking agent (F) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the crosslinking agent (F) is used, the content of the crosslinking agent (F) in the composition (III-1) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the content of the polymer component (A). By setting the content of the crosslinking agent (F) to the lower limit or more, the effect of using the crosslinking agent (F) can be more remarkably obtained. Further, by making the content of the crosslinking agent (F) the upper limit value or less, the excessive use of the crosslinking agent (F) is suppressed.
[ energy ray-curable resin (G) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain an energy ray-curable resin (G). By incorporating the energy ray-curable resin (G) into the film for forming a thermosetting protective film, the properties can be changed by irradiation with an energy ray.
The energy ray-curable resin (G) is obtained by polymerizing (curing) an energy ray-curable compound.
Examples of the energy ray-curable compound include compounds having at least 1 polymerizable double bond in the molecule, and acrylate compounds having a (meth) acryloyl group are preferable.
Examples of the acrylic ester-based compound include (meth) acrylates having a chain-like aliphatic skeleton such as trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate; cyclic aliphatic skeleton-containing (meth) acrylates such as dicyclopentyl di (meth) acrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di (meth) acrylate; an oligoester (meth) acrylate; a urethane (meth) acrylate oligomer; epoxy-modified (meth) acrylates; a polyether (meth) acrylate other than the polyalkylene glycol (meth) acrylate; itaconic acid oligomers, and the like.
The weight average molecular weight of the energy ray-curable compound is preferably 100 to 30000, more preferably 300 to 10000.
The energy ray-curable compound used for polymerization may be one kind only, or two or more kinds, and in the case of two or more kinds, a combination and a ratio thereof may be arbitrarily selected.
The energy ray-curable resin (G) contained in the composition (III-1) and the film for forming a thermosetting protective film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the energy ray-curable resin (G) is used, the content of the energy ray-curable resin (G) in the composition (III-1) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass, based on the total mass of the composition (III-1).
[ photopolymerization initiator (H) ]
When the composition (III-1) and the film for forming a thermosetting protective film contain the energy ray-curable resin (G), a photopolymerization initiator (H) may be contained in order to more efficiently perform the polymerization reaction of the energy ray-curable resin (G).
Examples of the photopolymerization initiator (H) in the composition (III-1) include the same photopolymerization initiators as those that can be contained in the adhesive composition described above.
The composition (III-1) and the film for forming a thermosetting protective film may contain only one kind of photopolymerization initiator (H), or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
When the photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III-1) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, relative to 100 parts by mass of the energy ray-curable resin (G).
[ colorant (I) ]
The composition (III-1) and the film for forming a thermosetting protective film preferably contain a colorant (I). By using the colorant (I), a film for forming a protective film having a light transmittance of 365nm of 0.3% or less can be produced more easily.
Examples of the colorant (I) include known colorants such as inorganic pigments, organic pigments, and organic dyes.
Examples of the organic pigments and organic dyes include aminium (aminium) pigments, cyanine pigments, merocyanine pigments, croconium (croconium) pigments, squarylium (squarylium) pigments, azulenium (azulenium) pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalimide (naphthaloctamide) pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt pigments), dithiol metal complex pigments, indole pigments, triarylmethane pigments, anthraquinone pigments, naphthol pigments, methine pigments, and methine pigments, Benzimidazolone pigments, pyranthrone pigments, threne pigments and the like.
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.
The composition (III-1) and the film for forming a thermosetting protective film may contain only one kind of the colorant (I), or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
When the colorant (I) is used, the content of the colorant (I) in the thermosetting protective film-forming film may be appropriately adjusted according to the purpose. For example, by adjusting the content of the colorant (I) in the thermosetting protective film-forming film and adjusting the light transmittance (365nm), the light transmittance (555nm), and the light transmittance (800nm) of the thermosetting protective film-forming film, the ultraviolet-shielding property and the visibility at the time of laser printing can be adjusted for the thermosetting protective film-forming film or the cured product thereof. Further, by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film, the design of the protective film can be improved, and grinding marks on the back surface of the semiconductor wafer and laser printing for process control can be made less visible. In view of these points, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all the components except the solvent (i.e., the ratio of the content of the colorant (I) in the film for forming a thermosetting protective film to the total mass of the film for forming a thermosetting protective film) is preferably 1.0 to 12% by mass, more preferably 1.0 to 9% by mass, and particularly preferably 1.0 to 7% by mass. By setting the ratio to the lower limit or more, the effect of using the colorant (I) can be obtained more remarkably. Further, by making the ratio the upper limit value or less, the excessive use of the colorant (I) is suppressed.
[ general additive (J) ]
The composition (III-1) and the film for forming a thermosetting protective film may contain the general-purpose additive (J) within a range not to impair the effects of the present invention.
The general-purpose additive (J) may be a known additive, and may be appropriately selected according to the purpose, and is not particularly limited, and preferable additives include a plasticizer, an antistatic agent, an antioxidant, a gettering agent (getterng agent), an ultraviolet absorber, and the like.
The composition (III-1) and the film for forming a thermosetting protective film may contain only one kind of the general-purpose additive (J), or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the general-purpose additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited and may be appropriately selected depending on the purpose.
[ solvent ]
The composition (III-1) preferably further contains a solvent. The composition (III-1) containing a solvent was excellent in handling properties.
The solvent is not particularly limited, and preferable examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (also referred to as 2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (i.e., compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone, and the like.
The solvent contained in the composition (III-1) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
As a more preferable solvent contained in the composition (III-1), methyl ethyl ketone, toluene, ethyl acetate and the like can be mentioned, since the components contained in the composition (III-1) can be mixed more uniformly.
The content of the solvent in the composition (III-1) is not particularly limited, and may be appropriately selected depending on the kind of the component other than the solvent, for example.
< method for producing composition for forming thermosetting protective film >
The thermosetting protective film-forming composition such as composition (III-1) can be obtained by blending the respective components constituting the composition.
The thermosetting protective film-forming composition can be prepared, for example, by the same method as the adhesive composition described above, except that the kinds of blending components are different.
Energy ray-curable protective film-forming film
The curing conditions for forming the protective film by attaching the energy ray-curable protective film-forming film to a target position of a workpiece and curing the film with an energy ray are not particularly limited as long as the protective film has a degree of curing sufficient to exhibit its function, and may be appropriately selected depending on the type of the energy ray-curable protective film-forming film.
For example, the illuminance of the energy ray when the energy ray-curable protective film-forming film is cured with an energy ray may be 120 to 280mW/cm2And may be a lower illuminance. The quantity of the energy ray during curing may be 100 to 1000mJ/cm2A lower light amount is also possible.
Examples of the film for forming an energy ray-curable protective film include a film containing an energy ray-curable component (a), and preferably containing an energy ray-curable component (a) and a filler.
In the film for forming an energy ray-curable protective film, the energy ray-curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive.
< composition for Forming energy ray-curable protective film (IV-1) >
Examples of a preferable energy ray-curable composition for forming a protective film include an energy ray-curable composition for forming a protective film (IV-1) containing the energy ray-curable component (a) (in the present specification, this may be abbreviated as "composition (IV-1)") and the like.
[ energy ray-curable component (a) ]
The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray, and is used for imparting film formability, flexibility, or the like to the energy ray-curable protective film-forming film, and for forming a hard protective film after curing.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000, and a compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000. At least a portion of the polymer (a1) may or may not be crosslinked by a crosslinking agent.
(a polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000.)
Examples of the polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000 include an acrylic resin (a1-1) obtained by reacting an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound and an energy ray-curable compound (a12) having an energy ray-curable group such as a group capable of reacting with the functional group and an energy ray-curable double bond.
Examples of the functional group capable of reacting with a group of another compound include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group in which 1 or 2 hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom), an epoxy group, and the like. However, the functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of a circuit of a workpiece, a workpiece processed product, or the like.
Among them, the functional group is preferably a hydroxyl group.
Acrylic Polymer having functional group (a11)
Examples of the acrylic polymer (a11) having the functional group include polymers obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group, and polymers obtained by further copolymerizing a monomer other than an acrylic monomer (non-acrylic monomer) in addition to these monomers.
The acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known polymerization method may be used.
Examples of the acrylic monomer having the functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and non (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols having no (meth) acryloyl skeleton).
Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of said ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer.
The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the acrylic monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, n-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth), And alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is a carbon number of 1 to 18, such as tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearate (meth) acrylate).
Examples of the acrylic monomer having no functional group include (meth) acrylates containing an alkoxyalkyl group such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate; aromatic group-containing (meth) acrylates such as aryl (meth) acrylates including phenyl (meth) acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; and non-crosslinkable (meth) acrylic esters having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
The non-acrylic monomer constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer (a11), the proportion (content) of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the polymer is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. By making the ratio in the above range, the content of the energy ray-curable group in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) can easily adjust the degree of curing of the protective film to a preferred range.
The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (IV-1), the proportion of the content of the acrylic resin (a1-1) to the total content of components other than the solvent (i.e., the proportion of the content of the acrylic resin (a1-1) in the energy ray-curable protective film-forming film to the total mass of the film) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass.
Energy ray-curable compound (a12)
The energy ray-curable compound (a12) preferably has one or two or more groups selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a group capable of reacting with the functional group of the acrylic polymer (a11), and more preferably has an isocyanate group as the group. When the energy ray-curable compound (a12) has an isocyanate group as the group, for example, the isocyanate group is easily reacted with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
The number of the energy ray-curable groups of the energy ray-curable compound (a12) in one molecule thereof is not particularly limited, and may be appropriately selected in consideration of physical properties such as shrinkage ratio required for the intended protective film.
For example, the energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups in one molecule, and more preferably has 1 to 3 energy ray-curable groups.
Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloxymethyl) ethyl isocyanate;
An acryloyl monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
and an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth) acrylate.
Among them, the energy ray-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.
The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the content ratio is in the above range, the adhesive strength of the cured product of the energy ray-curable protective film-forming film is further increased. In addition, when the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the proportion of the content is 100 mol%, but when the energy ray-curable compound (a12) is a polyfunctional compound (having two or more groups in one molecule), the upper limit of the proportion of the content may exceed 100 mol%.
The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000 to 2000000, more preferably 300000 to 1500000.
The "weight average molecular weight" is the weight average molecular weight described above.
When at least a portion of the polymer (a1) is crosslinked by a crosslinking agent, the polymer (a1) may be: the polymer which is not any of the above-mentioned monomers explained as monomers constituting the acrylic polymer (a11) and has a group which reacts with a crosslinking agent, and which is crosslinked at the group which reacts with the crosslinking agent may be: a polymer crosslinked at a group which reacts with the functional group from the energy ray-curable compound (a 12).
The polymer (a1) contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
(Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000.)
Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000 include groups containing an energy ray-curable double bond, and preferable examples thereof include a (meth) acryloyl group, a vinyl group and the like.
As long as the above conditions are satisfied, the compound (a2) is not particularly limited, and examples thereof include a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, a phenol resin having an energy ray-curable group, and the like.
Examples of the low molecular weight compound having an energy ray-curable group in the compound (a2) include polyfunctional monomers and oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylate-based compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxypolyethoxy) phenyl ] propane, ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxydiethoxy) phenyl ] propane, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, 2-bis [4- ((meth) acryloyloxypropyloxy) phenyl ] propane, tricyclodecanedimethanol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and mixtures thereof, Bifunctional (meth) acrylates such as 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and 2-hydroxy-1, 3-di (meth) acryloyloxypropane;
Polyfunctional (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) isocyanurate, caprolactone-modified tris- (2- (meth) acryloyloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, and dipentaerythritol hexa (meth) acrylate;
and polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.
As the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group in the compound (a2), for example, the resins described in japanese patent application laid-open No. 2013-194102 "paragraph 0043 and the like can be used. The above resin also belongs to a resin constituting a thermosetting component described later, but it is used as the compound (a2) in the present invention.
The weight average molecular weight of the compound (a2) is preferably 100 to 30000, more preferably 300 to 10000.
The compound (a2) contained in the composition (IV-1) and the energy ray-curable protective film-forming film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
[ Polymer (b) having no energy ray-curable group ]
When the composition (IV-1) and the film for forming an energy ray-curable protective film contain the compound (a2) as the energy ray-curable component (a), it is further preferable to contain a polymer (b) having no energy ray-curable group.
The polymer (b) may or may not be at least partially crosslinked with a crosslinking agent.
Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins.
Among them, the polymer (b) is preferably an acrylic polymer (hereinafter, it may be abbreviated as "acrylic polymer (b-1)").
The acrylic polymer (b-1) is a known component, and may be, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers and one or more monomers (non-acrylic monomers) other than the acrylic monomers.
Examples of the acrylic monomer constituting the acrylic polymer (b-1) include alkyl (meth) acrylates, (meth) acrylates having a cyclic skeleton, glycidyl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylates, and substituted amino group-containing (meth) acrylates. Wherein "substituted amino group" is the previously described substituted amino group.
Examples of the alkyl (meth) acrylate include the same alkyl (meth) acrylates as those of the acrylic monomers having no functional group (e.g., alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester has a chain structure of 1 to 18 carbon atoms) constituting the acrylic polymer (a11) described above.
Examples of the (meth) acrylate having the cyclic skeleton include cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate, and the like.
Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate and the like.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the substituted amino group-containing (meth) acrylate include N-methylaminoethyl (meth) acrylate and the like.
Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
Examples of the polymer (b) having no energy ray-curable group, at least a part of which is crosslinked by a crosslinking agent, include polymers obtained by reacting a reactive functional group in the polymer (b) with a crosslinking agent.
The reactive functional group is not particularly limited as long as it is appropriately selected according to the kind of the crosslinking agent and the like. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amino group, and the like, and among them, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amino group, and an amide group, and among them, a carboxyl group having high reactivity with an epoxy group is preferable. However, the reactive functional group is preferably a group other than a carboxyl group from the point of preventing corrosion of the circuit of the workpiece or the workpiece processed product.
Examples of the polymer (b) having the reactive functional group and not having an energy ray-curable group include polymers obtained by polymerizing a monomer having at least the reactive functional group. In the case of the acrylic polymer (b-1), a monomer having the reactive functional group may be used as either one or both of the acrylic monomer and the non-acrylic monomer described above as a monomer constituting the acrylic polymer (b-1). Examples of the polymer (b) having a hydroxyl group as a reactive functional group include polymers obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and polymers obtained by polymerizing a monomer in which 1 or 2 or more hydrogen atoms in the above-mentioned acrylic monomer or non-acrylic monomer are substituted with the reactive functional group.
In the polymer (b) having a reactive functional group, the proportion (content) of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural units constituting the polymer is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. By setting the ratio in the above range, the degree of crosslinking in the polymer (b) becomes a more preferable range.
The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably 10000 to 2000000, more preferably 100000 to 1500000, from the viewpoint of improving the film-forming property of the composition (IV-1). The "weight average molecular weight" is the weight average molecular weight described above.
The composition (IV-1) and the energy ray-curable protective film-forming film may contain only one kind of polymer (b) having no energy ray-curable group, or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
The composition (IV-1) may be a composition containing either one or both of the polymer (a1) and the compound (a 2). When the composition (IV-1) contains the compound (a2), it preferably further contains a polymer (b) having no energy ray-curable group, and in this case, it further preferably contains the compound (a 1). The composition (IV-1) may contain the polymer (a1) and the polymer (b) having no energy ray-curable group, in addition to the compound (a 2).
When the composition (IV-1) contains the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the content of the compound (a2) in the composition (IV-1) is preferably 10 to 400 parts by mass, more preferably 30 to 350 parts by mass, relative to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group.
In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (i.e., the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total mass of the film in the energy ray-curable protective film-forming film) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. When the ratio of the content of the energy ray-curable component is in the above range, the energy ray-curability of the energy ray-curable protective film-forming film is more preferable.
The composition (IV-1) may contain, in addition to the energy ray-curable component, one or more components selected from the group consisting of a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general-purpose additive, depending on the purpose.
The thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant and the general-purpose additive in the composition (IV-1) may be the same components as those of the thermosetting component (B), the filler (D), the coupling agent (E), the crosslinking agent (F), the photopolymerization initiator (H), the colorant (I) and the general-purpose additive (J) in the composition (III-1), respectively.
For example, by using the composition (IV-1) containing the energy ray-curable component and the thermosetting component, the adhesion of the formed energy ray-curable protective film-forming film to an adherend is improved by heating, and the strength of the protective film formed from the energy ray-curable protective film-forming film is also improved.
By using the composition (IV-1) containing the energy ray-curable component and the colorant, the formed energy ray-curable protective film-forming film exhibits the same effects as those of the case where the thermosetting protective film-forming film described above contains the colorant (I).
In the composition (IV-1), the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant and the general-purpose additive may be used singly or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
The content of the thermosetting component, the filler, the coupling agent, the crosslinking agent, the photopolymerization initiator, the colorant and the general-purpose additive in the composition (IV-1) is not particularly limited as long as it is appropriately adjusted according to the purpose.
The composition (IV-1) preferably contains a solvent because the handling properties are improved by dilution.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those in the composition (III-1).
The composition (IV-1) may contain only one solvent, or may contain two or more solvents. The content of the solvent in the composition (IV-1) is not particularly limited, and may be appropriately selected depending on the kind of the component other than the solvent, for example.
< method for producing composition for forming energy ray-curable protective film >
The energy ray-curable composition for forming a protective film such as the composition (IV-1) can be obtained by blending the respective components constituting the composition.
The energy ray-curable composition for forming a protective film can be prepared, for example, by the same method as the adhesive composition described above, except that the kinds of the blending components are different.
Non-curable protective film-forming film
A preferable non-curable protective film-forming film includes, for example, a film containing a thermoplastic resin and a filler.
< composition for Forming non-curable protective film (V-1) >
Examples of a preferable composition for forming a non-curable protective film include the composition (V-1) for forming a non-curable protective film (hereinafter, simply referred to as "composition (V-1)") containing the thermoplastic resin and the filler.
[ thermoplastic resin ]
The thermoplastic resin is not particularly limited.
More specifically, the thermoplastic resin may be the same as the non-curable resin such as an acrylic resin, a polyester, a polyurethane, a phenoxy resin, polybutene, polybutadiene, or polystyrene, which is the component contained in the composition (III-1).
The thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (V-1), the proportion of the content of the thermoplastic resin with respect to the total content of the components other than the solvent (i.e., the proportion of the content of the thermoplastic resin in the non-curable protective film-forming film with respect to the total mass of the non-curable protective film-forming film) is preferably 25 to 75% by mass.
[ Filler ]
The filler-containing film for forming a non-curable protective film exhibits the same effects as those of the filler-containing film for forming a thermosetting protective film.
Examples of the filler contained in the composition (V-1) and the non-curable film for forming a protective film include the same fillers as the filler (D) contained in the composition (III-1) and the film for forming a thermosetting protective film.
The composition (V-1) and the non-curable protective film-forming film may contain only one filler, or may contain two or more fillers, and when the amount of the filler is two or more, the combination and ratio thereof may be arbitrarily selected.
In the composition (V-1), the proportion of the content of the filler relative to the total content of all the components except the solvent (i.e., the proportion of the content of the filler in the non-curable protective film-forming film relative to the total mass of the non-curable protective film-forming film) is preferably 25 to 75% by mass. By setting the ratio within the above range, the thermal expansion coefficient of the non-curable protective film-forming film (i.e., the protective film) can be more easily adjusted as in the case of using the composition (III-1).
The composition (V-1) may contain other components depending on the purpose, in addition to the thermoplastic resin and the filler.
The other components are not particularly limited and may be arbitrarily selected according to the purpose.
For example, by using the composition (V-1) containing the thermoplastic resin and the colorant, the formed film for forming a non-curable protective film (in other words, protective film) exhibits the same effects as those obtained when the thermosetting film for forming a protective film contains the colorant (I) as described above.
In the composition (V-1), the other components may be used singly or in combination of two or more, and when two or more are used simultaneously, the combination and ratio thereof may be arbitrarily selected.
The content of the other components in the composition (V-1) is not particularly limited as long as it is appropriately adjusted according to the purpose.
The composition (V-1) is preferably further containing a solvent because the handling properties are improved by dilution.
Examples of the solvent contained in the composition (V-1) include the same solvents as those in the composition (III-1).
The composition (V-1) may contain only one kind of solvent, or may contain two or more kinds of solvents.
The content of the solvent in the composition (V-1) is not particularly limited, and may be appropriately selected depending on the kind of components other than the solvent, for example.
< method for producing composition for forming non-curable protective film >
The composition for forming a non-curable protective film such as the composition (V-1) can be obtained by blending the respective components for constituting the composition.
The composition for forming a non-curable protective film can be prepared, for example, by the same method as the adhesive composition described above, except that the kind of the blending component is different.
One embodiment of the composite sheet for forming a protective film includes, for example, a composite sheet for forming a protective film including a support sheet and a film for forming a protective film provided on one surface of the support sheet, wherein the protective film has a transmittance of light having a wavelength of 365nm of 0.3% or less, the protective film has a transmittance of light having a wavelength of 555nm of 5% or less, the protective film has a transmittance of light having a wavelength of 800nm of less than 20%, the support sheet has a transmittance of light having a wavelength of 365nm of 40 to 97%, the protective film or a cured product thereof has an adhesion of less than 370mN/25mm to the support sheet, and a content of a colorant is 1.0 to 12% by mass based on the total mass of the protective film.
Manufacturing method of composite sheet for protective film formation
The composite sheet for forming a protective film can be produced by laminating the above layers so as to have a corresponding positional relationship, and adjusting the shape of a part or all of the layers as required. The method of forming each layer is the method of forming described above.
For example, when the adhesive layer is laminated on a substrate in the production of a support sheet, the adhesive composition may be applied to the substrate and dried as necessary.
In addition, the adhesive layer can be laminated on the substrate by a method in which the adhesive composition is applied to the release film and dried as necessary to form the adhesive layer on the release film and the exposed surface of the adhesive layer is bonded to one surface of the substrate, and in this case, the adhesive composition is preferably applied to the release-treated surface of the release film.
Although the case of laminating an adhesive layer on a substrate has been described above as an example, the above-described method can be applied to a case of laminating an intermediate layer or the other layer on a substrate.
On the other hand, for example, when a film for forming a protective film is further laminated on an adhesive layer laminated on a base material, the film for forming a protective film can be directly formed by applying a composition for forming a protective film on the adhesive layer. In the same manner, a layer other than the film for forming a protective film may be laminated on the adhesive layer using the composition for forming the layer. In this manner, when a new layer (hereinafter, abbreviated as "second layer") is formed on any layer (hereinafter, abbreviated as "first layer") already laminated on the base material to form a continuous two-layer laminated structure (in other words, a laminated structure of the first layer and the second layer), a method of coating the composition for forming the second layer on the first layer and drying it as necessary can be applied.
However, the second layer is preferably formed in advance on the release film using a composition for forming the layer, and the exposed surface of the formed second layer on the side opposite to the side in contact with the release film is bonded to the exposed surface of the first layer, thereby forming a continuous two-layer laminated structure. In this case, the composition is preferably applied to the release-treated surface of the release film. After the laminated structure is formed, the release film may be removed as needed.
Here, although the case where the film for forming a protective film is laminated on the adhesive agent layer is exemplified, a lamination structure to be targeted when, for example, an intermediate layer or the other layer is laminated on the adhesive agent layer can be arbitrarily selected.
In this manner, since all layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of forming the layers on the release film in advance and bonding the layers to the surface of the target layer, the composite sheet for forming a protective film can be produced by appropriately selecting the layers to be subjected to the above steps as needed.
The composite sheet for forming a protective film is generally stored in a state in which a release film is bonded to the surface of the outermost layer (for example, a film for forming a protective film) on the side opposite to the support sheet. Therefore, the composite sheet for forming a protective film with a release film can be obtained by applying a composition for forming the outermost layer, such as a composition for forming a protective film, to the release film (preferably, the release-treated surface thereof) and drying the composition as necessary to form the outermost layer on the release film, and laminating the remaining layers on the exposed surface of the layer on the opposite side to the side in contact with the release film by any of the above-mentioned methods, while maintaining the state in which the release film is bonded without removing the release film.
Manufacturing method of workpiece with protective film (method of Using composite sheet for Forming protective film)
The composite sheet for forming a protective film is useful for producing the workpiece with a protective film.
As an example of a method for producing a work piece with a protective film, which comprises a protective film at an arbitrary position of the work piece, there is a method for producing a protective film, which comprises the following steps, and which is obtained by adhering the protective film-forming film to the work piece and then curing the film without curing the film, or a cured product obtained by curing the film, as a protective film: a sticking step of sticking a protective film forming film in the protective film forming composite sheet to a target position of a workpiece to thereby prepare a laminated body in which the protective film forming composite sheet is provided (laminated) on the workpiece; a curing step of curing the protective film-forming film as needed after the attaching step; a printing step of irradiating the protective film-forming film or the cured product thereof in the protective film-forming composite sheet in the laminate with laser light from the outside of the protective film-forming composite sheet on the side of the support sheet through the support sheet after the attaching step, thereby printing on the protective film-forming film or the cured product thereof; and a processing step of processing the workpiece after the printing step to produce a workpiece processed product.
As an example of a method for manufacturing a semiconductor chip with a protective film, which is a work with a protective film when the work is a semiconductor wafer, there is a method for manufacturing a semiconductor chip with a protective film, which includes the following steps, and in which the protective film-forming film is attached to the semiconductor wafer and then cured without being cured, or a cured product obtained by curing the protective film is used as the protective film: a sticking step of sticking a film for forming a protective film in the composite sheet for forming a protective film to the back surface of a semiconductor wafer to form a laminate in which the composite sheet for forming a protective film is provided on the back surface of the semiconductor wafer; a curing step of curing the protective film-forming film as needed after the attaching step; a printing step of irradiating the protective film-forming film or the cured product thereof in the protective film-forming composite sheet in the laminate with laser light from the outside of the protective film-forming composite sheet on the side of the support sheet through the support sheet after the attaching step, thereby printing on the protective film-forming film or the cured product thereof; a dividing/cutting step of dividing the semiconductor wafer after the printing step to produce semiconductor chips, and further cutting the protective film-forming film or the cured product thereof; and a pick-up step of separating the semiconductor chip provided with the cut protective film-forming film or the cured product thereof from the supporting sheet and picking up the semiconductor chip.
In the manufacturing method, when the workpiece is a semiconductor wafer, the workpiece described above can be used.
In the above-described manufacturing method, by using the composite sheet for forming a protective film of the present embodiment, even when the laser beam having a short wavelength such as 266nm is irradiated, it is possible to favorably print on the film for forming a protective film or the cured product thereof in the composite sheet for forming a protective film. The printing can be recognized well from the outside of the protective film forming composite sheet on the side of the support sheet through the support sheet.
The production method can be classified into a production method in which the curing step is provided (in the present specification, this may be referred to as "production method (1)") and a production method in which the curing step is not provided (in the present specification, this may be referred to as "production method (2)").
These production methods will be described in order below.
Method (1) for producing an infant food
The manufacturing method (1) is a manufacturing method of a workpiece with a protective film, which includes a protective film at an arbitrary position of the workpiece, and includes the following steps, and a cured product obtained by curing the protective film-forming film adhered to the workpiece is used as the protective film: a sticking step of sticking a film for forming a protective film in the composite sheet for forming a protective film to a target position of a workpiece to thereby prepare a laminated body in which the composite sheet for forming a protective film is provided (laminated) on the workpiece; a curing step of curing the protective film-forming film after the attaching step; a printing step of irradiating the protective film-forming film or the cured product thereof in the protective film-forming composite sheet in the laminate with laser light from the outside of the protective film-forming composite sheet on the side of the support sheet through the support sheet after the attaching step, thereby printing on the protective film-forming film or the cured product thereof; and a processing step of processing the workpiece after the printing step to produce a workpiece processed product.
Fig. 5 to 9 are sectional views schematically illustrating an example of the manufacturing method (1) when the workpiece is a semiconductor wafer. Here, a method for manufacturing the composite sheet 101 for forming a protective film shown in fig. 1 will be described.
< attaching step >
In the sticking step, the composite sheet 101 from which the release film 15 has been removed is used as the composite sheet 101 for forming a protective film, and as shown in fig. 5, the film 13 for forming a protective film in the composite sheet 101 for forming a protective film is stuck to the back surface 9b of the semiconductor wafer 9. This produces a laminate 901 including the semiconductor wafer 9 and the composite sheet 101 for forming a protective film provided on the back surface 9b thereof.
In the attaching step, the protective film forming film 13 is heated and softened, and is attached to the semiconductor wafer 9.
Here, in the semiconductor wafer 9, bumps and the like on the circuit forming surface 9a are not shown.
The reference numeral 13b denotes a surface (in this specification, it may be referred to as a "second surface") of the protective film-forming film 13 opposite to the first surface 13a (in other words, on the adhesive agent layer 12 side).
The back surface of the semiconductor wafer 9 may be ground to set the thickness thereof to a target value. That is, the back surface 9b of the semiconductor wafer 9 may be a ground surface.
In the semiconductor wafer 9, it is preferable that no through groove is present between the circuit forming surface 9a and the back surface 9 b.
< curing step >
In the curing step after the attachment step, as shown in fig. 6, the protective film-forming film 13 is cured.
Here, a case where the curing step is performed before the printing step is shown.
In the present embodiment, a cured product obtained by curing the protective film forming film 13 attached to the semiconductor wafer 9 is used as the protective film regardless of cutting.
By performing the curing step, the composite sheet 101 for forming a protective film becomes a composite sheet 1011 for forming a protective film in which the film 13 for forming a protective film becomes a cured product 13', and a cured laminate 9011 including the semiconductor wafer 9 and the composite sheet 1011 for forming a protective film provided on the back surface 9b thereof is obtained.
Reference numeral 13a 'denotes a first surface of the cured product 13' corresponding to the first surface 13a of the protective film forming film 13, and reference numeral 13b 'denotes a second surface of the cured product 13' corresponding to the second surface 13b of the protective film forming film 13.
In the curing step, when the protective film-forming film 13 is thermosetting, the protective film-forming film 13 is heated to form a cured product 13'. When the protective film forming film 13 is energy ray-curable, the protective film forming film 13 is irradiated with an energy ray through the support sheet 10, thereby forming a cured product 13'.
In the curing step, the curing conditions of the protective film-forming film 13, that is, the heating temperature and heating time in the thermal curing and the illuminance and light amount of the energy ray in the energy ray curing are as described above.
< printing step >
In the printing step after the sticking step, as shown in fig. 7, the cured product 13 'in the protective film forming composite sheet 1011 in the cured laminate 9011 is irradiated with the laser L from the outside of the protective film forming composite sheet 1011 on the side of the support sheet 10 through the support sheet 10, thereby printing on the cured product 13'. Printing (not shown) is performed on the second surface 13b 'of the cured product 13'.
By performing the printing step, the protective film forming composite sheet 1011 becomes a protective film forming composite sheet 1012 having the printed cured product 13', and a printed and cured laminate 9012 including the semiconductor wafer 9 and the protective film forming composite sheet 1012 provided on the back surface 9b thereof is obtained.
The wavelength of the laser light L is preferably shorter than conventional wavelengths, and more preferably 266 nm.
< dividing/cutting step >
In the dividing/cutting step after the printing step, as shown in fig. 8, the semiconductor wafer 9 is divided to produce semiconductor chips 9 ', and the cured product 13' is further cut.
By performing the dividing/cutting step, a plurality of semiconductor chips 91 with a protective film, each of which is composed of the semiconductor chip 9 'and the cut cured product 130' provided on the back surface 9b 'of the semiconductor chip 9', are obtained. These semiconductor chips 91 with protective films are all arranged on 1 support sheet 10, and these semiconductor chips 91 with protective films and the support sheet 10 constitute a semiconductor chip group 910 with protective films.
The reference numeral 130a 'denotes a first surface of the cured product 130' after cutting corresponding to the first surface 13a 'of the cured product 13', and the reference numeral 130b 'denotes a second surface of the cured product 130' after cutting corresponding to the second surface 13b 'of the cured product 13'.
Reference numeral 9a 'denotes a circuit forming surface of the semiconductor chip 9' corresponding to the circuit forming surface 9a of the semiconductor wafer 9.
The semiconductor chips 9' can be produced by dividing the semiconductor wafer 9 (in other words, by singulation) by a known method.
As a method of dividing the semiconductor wafer 9, for example, blade dicing in which the semiconductor wafer 9 is diced using a blade; laser dicing for dicing the semiconductor wafer 9 by laser irradiation; a method of cutting into a semiconductor wafer such as water dicing of the semiconductor wafer 9 cut by spraying water containing an abrasive.
In applying these methods, for example, the semiconductor wafer 9 is divided and the cured product 13 'is cut at the same time, so that the division of the semiconductor wafer 9 and the cutting of the cured product 13' are performed at the same time.
As a method of dividing the semiconductor wafer 9, a method other than the above-described method of cutting into a semiconductor wafer may be mentioned.
That is, in this method, first, a position to be divided is set in the semiconductor wafer 9, and a laser beam is irradiated so as to be focused on the position as a focal point, thereby forming a modified layer in the semiconductor wafer 9. Unlike other positions of the semiconductor wafer, the modified layer of the semiconductor wafer is modified by irradiation with laser light, and the strength thereof is weakened. Therefore, by applying a force to the semiconductor wafer 9, cracks are generated in the modified layer inside the semiconductor wafer 9 along the direction of both sides of the semiconductor wafer 9, and become starting points for dividing (cutting) the semiconductor wafer 9. Then, a force is applied to the semiconductor wafer 9 to divide the semiconductor wafer 9 at the modified layer portion, thereby forming a semiconductor chip. The method of dividing the semiconductor wafer 9 accompanying the formation of the modified layer is called a stead Dicing (registered trademark).
For example, the semiconductor wafer on which the modified layer is formed may be expanded in a direction parallel to the surface thereof and divided by applying a force. In this way, when the method of expanding the semiconductor wafer is applied, the semiconductor wafer 9 and the cured product 13 ' of the protective film forming film are expanded together to cut the cured product 13 ' at the same time, whereby the division of the semiconductor wafer 9 and the cutting of the cured product 13 ' can be performed together. The cutting by expanding the cured product 13' is preferably performed at a low temperature of-20 to 5 ℃.
When the division of the semiconductor wafer 9 and the cutting of the cured product 13 'are not performed simultaneously, the cutting of the cured product 13' may be performed by a known method in addition to the division of the semiconductor wafer 9.
< picking-up Process >
In the pickup step after the dividing/cutting step, as shown in fig. 9, the semiconductor chip 9 '(semiconductor chip 91 with a protective film) having the cured product 130' after cutting is separated from the support sheet 10 and picked up. Wherein the direction of the pick-up is indicated by arrow I.
The pickup of the semiconductor chip 91 with the protective film can be performed by a known method. For example, as the separation means 8 for separating the semiconductor chip 91 with the protective film from the support sheet 10, a vacuum chuck or the like can be mentioned. Note that, here, only the separation means 8 is not shown in cross section, which is also the case in the same drawing hereinafter.
Thereby, the semiconductor chip 91 with the target protective film is obtained.
In the semiconductor chip 91 with a protective film, which was the object of the printing process, such as the semiconductor chip with a protective film picked up, clear printing is maintained on the second surface 130b 'of the cured product 130' after cutting.
< timing of carrying out curing step >
Although the case where the curing step is performed between the pasting step and the printing step has been described above, the timing of performing the curing step in the production method (1) is not particularly limited. For example, in the production method (1), the curing step may be performed at any timing between the printing step and the dividing/cutting step, between the dividing/cutting step and the picking step, or after the picking step.
When the curing step is performed after the sticking step and the printing step, in the printing step, the protective film forming film 13 in the protective film forming composite sheet 101 in the laminate 901 shown in fig. 5 is irradiated with the laser light L from the outside of the protective film forming composite sheet 101 on the side of the support sheet 10 through the support sheet 10, thereby printing on the protective film forming film 13. Printing (not shown) is performed on the second surface 13b of the protective film forming film 13.
The printing step in this case can be performed by the same method as the printing step described above, except that the irradiation target of the laser beam L is the protective film forming film 13 and not the cured product 13' of the protective film forming film 13.
< other Process >
The manufacturing method (1) may have other steps not belonging to the above-described steps, in addition to the steps of the attaching step, the curing step, the printing step, the dividing/cutting step, and the picking-up step.
The type of the other step and the timing for performing the other step may be arbitrarily selected depending on the purpose, and is not particularly limited.
Method (2) for producing
As the manufacturing method (2), there is a manufacturing method of a work piece with a protective film, which includes a protective film at an arbitrary position of the work piece, and which includes the following steps, without curing the protective film-forming film attached to the work piece, to serve as the protective film: a sticking step of sticking a film for forming a protective film in the composite sheet for forming a protective film to a target position of a workpiece to thereby prepare a laminate in which the composite sheet for forming a protective film is provided (laminated) on the workpiece; a printing step of irradiating a protective film-forming film of the protective film-forming composite sheet in the laminate with laser light from outside the protective film-forming composite sheet on the side of the support sheet via the support sheet after the attaching step, thereby printing on the protective film-forming film; and a processing step of processing the workpiece after the printing step to produce a workpiece processed product.
The manufacturing method (2) is the same as the manufacturing method (1) and produces the same effects as the manufacturing method (1) except that the film for forming a protective film attached to the work is used as the protective film without the curing step, regardless of the kind of the work.
Although the method for producing a workpiece with a protective film has been described above mainly when the composite sheet 101 for forming a protective film shown in fig. 1 is used, the method for producing a workpiece with a protective film according to the present embodiment is not particularly limited.
For example, even when a composite sheet other than the composite sheet 101 for forming a protective film shown in fig. 1, such as the composite sheet for forming a protective film shown in fig. 2 to 4, is used, a workpiece with a protective film can be produced by the above-described production method in the same manner.
When the composite sheet for forming a protective film of another embodiment is used, the workpiece with a protective film can be produced by appropriately performing addition, change, deletion, and the like of the steps in the above-described production method, based on the difference in structure between the sheet and the composite sheet 101 for forming a protective film.
Manufacturing method of semiconductor device
After the work piece with the protective film is obtained by the above-described manufacturing method, a semiconductor device can be manufactured by using the work piece with the protective film by a known appropriate method according to the type thereof. For example, when the work piece with a protective film is a semiconductor chip with a protective film, the semiconductor chip with a protective film is flip-chip bonded to a circuit surface of a substrate, and then a semiconductor package is formed, and the semiconductor package is used to manufacture a target semiconductor device (not shown).
Examples
The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited to the examples shown below.
< raw materials for production of resin >
The following are formal names of raw materials for producing resins abbreviated in the present examples and comparative examples.
BA: acrylic acid butyl ester
MA: acrylic acid methyl ester
GMA: glycidyl methacrylate
HEA: 2-Hydroxyethyl acrylate
2 EHA: 2-ethylhexyl acrylate
MOI: 2-methacryloyloxyethyl isocyanate
< raw Material for production of composition for Forming protective film >
The raw materials used for preparing the composition for forming a protective film are shown below.
[ Polymer component (A) ]
(A) -1: acrylic acid Polymer (weight average molecular weight 300000, glass transition temperature-1 ℃ C.) copolymerized from BA (10 parts by mass), MA (70 parts by mass), GMA (5 parts by mass) and HEA (15 parts by mass)
[ thermosetting component (B1) ]
(B1) -1: bisphenol A epoxy resin ("jER 828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 to 194g/eq)
(B1) -2: bisphenol A epoxy resin ("jER 1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 800-900 g/eq)
(B1) -3: dicyclopentadiene type epoxy resin ("EPICLON HP-7200 HH" manufactured by DIC CORPORATION, epoxy equivalent 255-260 g/eq)
[ Heat-curing agent (B2) ]
(B2) -1: dicyandiamide ("ADEKA HARDNER EH-3636 AS" manufactured by ADEKA CORPORATION, thermally active latent epoxy resin curing agent having an active hydrogen amount of 21 g/eq; hereinafter, it may be abbreviated AS "DICY")
[ curing Accelerator (C) ]
(C) -1: 2-phenyl-4, 5-dihydroxymethylimidazole ("CURZOL 2 PHZ" manufactured by SHIKOKU CHEMICALS CORPORATION)
[ Filler (D) ]
(D) -1: silica filler (ADMATECHS Co., Ltd. "SC 2050 MA", silica filler surface-modified with epoxy compound, average particle diameter 0.5 μm)
(D) -2: silica Filler ("UF 310" manufactured by Tokuyama Corporation, average particle diameter 3 μm)
(D) -3: silica filler (SV-10 manufactured by Tatsumuri Co., Ltd., average particle diameter 8 μm)
[ coupling agent (E) ]
(E) -1: silane coupling agent (KBM 403 manufactured by Shin-Etsu Chemical Co., Ltd.)
(G) Inorganic colorant: carbon black (# MA650 manufactured by Mitsubishi Chemical Corporation, average particle diameter 28nm)
[ colorant (I) ]
(I) -1: carbon Black (manufactured by Mitsubishi Chemical Corporation, "MA 600B")
[ example 1]
Preparation of supporting sheet
< preparation of adhesive resin (I-2a) >
To an acrylic polymer having a weight average molecular weight of 600000, which was a copolymer of 2EHA (80 parts by mass) and HEA (20 parts by mass), was added MOI (an amount such that the total number of moles of isocyanate groups in the MOI was 0.75 times the total number of moles of hydroxyl groups from HEA in the acrylic polymer), and an addition reaction was performed in an air stream at 50 ℃ for 48 hours to obtain the objective adhesive resin (I-2a) -1.
Hereinafter, the acrylic polymer may be referred to as "adhesive resin (I-1a) -1".
< preparation of adhesive composition (I-2) >
An energy ray-curable adhesive composition (I-2) -1 was prepared which contained an adhesive resin (I-2a) -1(100 parts by mass), a hexamethylene diisocyanate crosslinking agent ("coronatol" manufactured by TOSOH CORPORATION) (6 parts by mass), Irgacure 184 "(1-hydroxycyclohexyl phenyl ketone) (3 parts by mass) manufactured by BASF CORPORATION as a photopolymerization initiator, Irgacure 127" (2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropyl) benzyl) -2-methylpropan-1-one) (3 parts by mass) manufactured by BASF CORPORATION, and further methyl ethyl ketone as a solvent, in a total concentration of all components except the solvent of 35% by mass. The contents of the components other than methyl ethyl ketone shown here are all the contents of the target product without a solvent.
< production of supporting sheet >
Using a release film (manufactured by Lintec Corporation, "SP-PET 381031" having a thickness of 38 μm) obtained by peeling one surface of a polyethylene terephthalate film by silicone treatment, the above-obtained adhesive composition (I-2) -1 was applied to the release-treated surface, and dried by heating at 100 ℃ for 2 minutes to form an energy ray-curable adhesive layer having a thickness of 5 μm.
Then, a polypropylene film (1) (80 μm thick, colorless) as a substrate was laminated on the exposed surface of the adhesive layer, thereby producing a laminate sheet in which the substrate, the adhesive layer, and the release film were laminated in this order in the thickness direction, that is, a support sheet with a release film.
The polypropylene film (1) was subjected to a tensile test at a tensile rate of 200mm/min in an environment of 23 ℃ in accordance with JIS K7127, and the Young's modulus was measured, and found to be 510 MPa.
Production of protective film-Forming film
< preparation of composition for Forming protective film (III-1) >
A thermosetting composition (III-1) -1 for forming a protective film having a total concentration of all components except a solvent of 45 mass% was obtained by dissolving or dispersing the polymer component (A) -1(150 mass parts), the thermosetting component (B1) -1(60 mass parts), the curing agent (B1) -2(10 mass parts), the thermal curing agent (B1) -3(30 mass parts), the thermal curing agent (B2) -1(2 mass parts), the curing accelerator (C) -1(2 mass parts), the filler (D) -1(320 mass parts), the coupling agent (E) -1(2 mass parts), and the colorant (I) -1(5.8 mass parts) in a mixed solvent of methyl ethyl ketone, toluene, and ethyl acetate and stirring at 23 ℃. The amounts of the components other than the mixed solvent described herein are the amounts of the target product without solvent.
< production of film for Forming protective film >
Using a release film (second release film, "SP-PET 381031", thickness 38 μm ", manufactured by linetec Corporation) obtained by peeling one surface of a polyethylene terephthalate film by silicone treatment, the above-obtained composition (III-1) -1 for forming a protective film was applied to the peeled surface, and dried at 100 ℃ for 2 minutes, thereby producing a thermosetting film for forming a protective film having a thickness of 15 μm.
Further, a release-treated surface of a release film (first release film, "SP-PET 381031 manufactured by Lintec Corporation," thickness 38 μm) was bonded to the exposed surface of the obtained protective film-forming film on the side not having the second release film, thereby obtaining a laminated film including a protective film-forming film, a first release film provided on one surface of the protective film-forming film, and a second release film provided on the other surface of the protective film-forming film.
Production of composite sheet for Forming protective film
The release film was removed from the support sheet obtained above. Further, the first release film was removed from the laminated film obtained above. Then, an exposed surface of the adhesive layer formed by removing the release film is bonded to an exposed surface of the protective film forming film formed by removing the first release film, thereby producing a protective film forming composite sheet in which a substrate, the adhesive layer, the protective film forming film, and a second release film are sequentially laminated in the thickness direction thereof.
Evaluation of support sheet
< measurement of light transmittance (365nm) of support sheet >
The release film was removed from the support sheet obtained above. Then, the support sheet was measured for transmittance of light having a wavelength region of 190 to 1200nm by using a spectrophotometer ("UV-VIS-NIR SPECTR OPH OTOMETER UV-3600" manufactured by SHIMADZU Corporation. In this case, a large sample chamber "MPC-3100" attached to the spectrophotometer and an integrating sphere incorporated in the spectrophotometer were used. Then, the transmittance of light (365nm) was calculated from the obtained measurement results. The results are shown in tables 1 and 2.
Evaluation of protective film Forming film
< measurement of transmittance of light (365nm), light (555nm) and light (800nm) >
The film for forming a protective film obtained above was heated at 130 ℃ for 2 hours in an oven to thermally cure the film for forming a protective film, thereby forming a protective film. The second release film was removed from the protective film, and the transmittance of light having a wavelength of 190 to 1200nm was measured using a spectrophotometer ("UV-VIS-NIR SPECTR OPHOTOMETER UV-3600" manufactured by SHIMADZUCORATION). In this case, the measurement was performed using a large sample chamber "MPC-3100" attached to the spectrophotometer, without using an integrating sphere incorporated in the spectrophotometer. Then, the transmittances of light (365nm), light (555nm) and light (800nm) were calculated from the obtained measurement results. The results are shown in tables 1 and 2.
Evaluation of composite sheet for Forming protective film
< evaluation of adhesion between protective film-forming film and support sheet after ultraviolet irradiation under Low-light UV irradiation >
The mirror surface of the silicon wafer and the surface of the protective film forming layer of the above-obtained composite sheet for forming a protective film were attached at room temperature of 70 ℃ using a film sticking machine (tape motor) (manufactured by Lintec Corporation, product name "Adwill RAD-3600F/12. Then, using a UV irradiation machine (OHMIYA ind. co., ltd., "UVI-1201 MB 7"), an illuminance of 5mW/cm was applied2Light quantity 100mJ/cm2The protective film-forming composite sheet was left standing for 20 minutes in an atmosphere of 23 ℃ and 50% RH (relative humidity) by UV irradiation from the substrate side.
After standing, an adhesive force measurement test was performed using a universal tester (manufactured by Shimadzu Corporation, product name "autograph AG-IS") under conditions of a peel angle of 180 ° and a peel speed of 0.3m/min, and a load at which the adhesive sheet was peeled from the protective film-forming layer was measured. The results are shown in tables 1 and 2.
< evaluation of pickup Property >
The release film was removed from the composite sheet for forming a protective film obtained above, and an 8-inch silicon wafer (thickness 100 μm, adhesion surface: finished product of dry polishing) was laminated on the adhesion surface of the exposed adhesive layer while heating to 70 ℃. Then, using a dicing apparatus ("DFD 6361" manufactured by DISCO Corporation), a silicon wafer was singulated into chips having a size of 8mm × 8mm using a dicing method by dicing with a blade having a feed speed of 30mm/sec, a rotation number of 30000rpm, and a blade of Z05-SD2000-D1-90 CC. At this time, the surface of the composite sheet for forming a protective film was deep-cut to a depth of 25 μm with a dicing blade.
Then, an operation of separating and picking up the silicon chip with the protective film from the supporting sheet was performed 10 times using a pickup device ("beam-D02" manufactured by Canon Machinery inc. The pickup at this time was performed by using 1 pin to jack up one silicon chip with a resin film, the jack-up speed was 20mm/s, and the jack-up amount was 200 μm. Then, the number of chips which could be picked up normally without generating cracks was checked, and the suitability for picking up semiconductor processed chips was evaluated according to the following evaluation criteria.
The results are shown in Table 1.
A: all chips can be picked up normally.
B: the number of chips that can be picked up normally is 6 or more.
C: 1-5 chips can be picked up normally.
D: the number of chips that can be picked up normally is 0.
< evaluation of masking Property of grinding trace on wafer >
The composite sheet for forming a protective film was attached to a polished surface of an 8-inch silicon wafer (surface: #2000, thickness 350 μm) at 70 ℃ to obtain a laminated body composed of the composite sheet for forming a protective film and the silicon wafer.
Then, the laminate was heated at 130 ℃ for 2 hours to thermally cure the protective film-forming layer in the composite sheet, thereby forming a protective film.
Then, the wafer with the protective film obtained by the heat curing was cooled and then irradiated with UV light from the support side (illuminance: 5 mW/cm) 2Light quantity of 100mJ/cm2) The support sheet is peeled from the wafer with the protective film.
Then, the wafer was observed from the protective film-attached surface of the wafer with the protective film, and whether or not the grinding mark of the wafer was visible through the protective film was evaluated by the following criteria.
(evaluation criteria)
5: even when the wafer was observed at a distance of 10cm from a fluorescent lamp, no grinding mark was observed at all.
4: when the wafer was observed at a distance of 10cm from the fluorescent lamp, a slight difference in the depth of the grinding mark was observed.
3: when the wafer was observed at a distance of 10cm from the fluorescent lamp, a significant difference in the depth of the grinding mark was observed.
2: when the wafer was observed at a distance of 10cm from the fluorescent lamp, the wafer was observed as grinding marks.
1: the grinding mark of the wafer can be seen without specially irradiating a fluorescent lamp or the like.
< evaluation of Ultraviolet (UV) screening Property >
The transmittance of light (365nm) of the composite sheet for protective film formation was calculated in the same manner as in the evaluation of the above film for protective film formation. Based on the obtained transmittance, Ultraviolet (UV) shielding properties were evaluated in the following evaluation criteria.
A: transmittance of light (365nm) of 0.05 or less
B: a transmittance of light (365nm) of more than 0.5 and 0.1 or less
C: a transmittance of light (365nm) of more than 0.1 and not more than 0.3
D: transmittance of light (365nm) greater than 0.3
Production and evaluation of support sheet, film for Forming protective film, and composite sheet for Forming protective film
[ example 2]
A support sheet, a film for forming a protective film, and a composite sheet for forming a protective film were produced and evaluated in the same manner as in example 1, except that 2.3 parts by mass of the colorant (I) -1 was used in producing the composition for forming a protective film. The results are shown in Table 1.
[ example 3]
A support sheet, a film for forming a protective film, and a composite sheet for forming a protective film were produced and evaluated in the same manner as in example 1, except that 1.7 parts by mass of the colorant (I) -1 was used in producing the composition for forming a protective film. The results are shown in Table 1.
[ example 4]
A support sheet, a film for forming a protective film, and a composite sheet for forming a protective film were produced and evaluated in the same manner as in example 1, except that 1.2 parts by mass of the colorant (I) -1 was used in producing the composition for forming a protective film. The results are shown in Table 1.
[ example 5]
A support sheet, a film for forming a protective film, and a composite sheet for forming a protective film were produced and evaluated in the same manner as in example 1, except that (B1) -1(60 parts by mass) and (B1) -3(40 parts by mass), which were thermosetting components, were used in the production of the composition for forming a protective film, and (D) -2(320 parts by mass) was used in place of the filler (D) -1(320 parts by mass). The results are shown in Table 1.
[ example 6]
A support sheet, a film for forming a protective film, and a composite sheet for forming a protective film were produced and evaluated in the same manner as in example 1, except that (B1) -1(70 parts by mass) and (B1) -3(30 parts by mass) were used as thermosetting components and (D) -3(320 parts by mass) was used instead of the filler (D) -1(320 parts by mass) in producing the composition for forming a protective film. The results are shown in Table 1.
Comparative example 1
A support sheet, a film for forming a protective film, and a composite sheet for forming a protective film were produced and evaluated in the same manner as in example 1, except that 0.6 part by mass of the colorant (I) -1 was used in producing the composition for forming a protective film. The results are shown in Table 2.
Comparative example 2
A support sheet, a protective film-forming film, and a protective film-forming composite sheet were produced in the same manner as in example 1, except that the coloring agent (I) -1 was not used in producing the protective film-forming composition, and evaluated. The results are shown in Table 2.
[ Table 1]
Figure BDA0002459953400000741
[ Table 2]
Figure BDA0002459953400000751
From the above results, it is clear that in examples 1 to 6, the transmittance of light (365nm) of the protective film-forming film was 0.3% or less, and the composite sheet for protective film formation was excellent in Ultraviolet (UV) shielding property. In contrast, the protective film-forming films of comparative examples 1 and 2 had a light (365nm) transmittance of more than 0.3%, and the composite sheet for forming a protective film had poor Ultraviolet (UV) shielding properties.
In addition, in examples 1 to 4, the illuminance was 5mW/cm2Light quantity 100mJ/cm2The protective film-forming film obtained by ultraviolet irradiation under the low-illuminance UV irradiation conditions has a tack force of less than 370mN/25mm with respect to the support sheet, and is excellent in pickup properties. In particular, the composite sheet for forming a protective film of example 1 was irradiated with ultraviolet rays under low-illuminance UV irradiation conditions, and the adhesion between the protective film-forming film and the support sheet was set to a low value of 105mN/25mm, and the pickup property was particularly excellent. The composite sheets for forming a protective film of examples 5 and 6 were irradiated with UV light at low illuminanceThe protective film-forming film obtained by ultraviolet irradiation has a low pick-up property because the adhesive force between the protective film-forming film and the support sheet is 370mN/25mm or more.
With respect to the grinding mark shielding properties of the composite sheet for forming a protective film, in examples 1 to 3, 5 and 6, the transmittance of light (555nm) of the film for forming a protective film was 5% or less, and the transmittance of light (800nm) was less than 20%. Therefore, the grinding mark masking property was evaluated as 4 or 5, and the grinding mark masking property was good. In example 4, the transmittance of light (555nm) of the protective film-forming film was 5% or less, but the transmittance of light (800nm) was 20%. Therefore, the grinding mark masking property was evaluated as 3, and the grinding mark masking property was slightly inferior to those of examples 1 to 3, 5 and 6. In contrast, in comparative examples 1 and 2, the transmittance of light (555nm) of the protective film-forming film was more than 5%, and the transmittance of light (800nm) was also 20% or more. Therefore, the evaluation of the grinding mark masking property was 1 or 2, and the grinding mark masking property was poor.
Industrial applicability
The invention can be used for manufacturing semiconductor devices.

Claims (5)

1. A composite sheet for forming a protective film, comprising a support sheet and a protective film-forming film provided on one surface of the support sheet, wherein the protective film-forming film has a transmittance of 0.3% or less for light having a wavelength of 365 nm.
2. The composite sheet for forming a protective film according to claim 1, wherein the support sheet comprises a base material and an adhesive layer provided on one surface of the base material,
the adhesive layer is disposed between the base material and the protective film-forming film,
the adhesive layer is an energy ray-curable adhesive layer.
3. The composite sheet for forming a protective film according to claim 1 or 2, wherein the adhesion between the film for forming a protective film or a cured product thereof and the supporting sheet is less than 370mN/25 mm.
4. A composite sheet for forming a protective film according to any one of claims 1 to 3, wherein the protective film-forming film has a transmittance of 5% or less for light having a wavelength of 555 nm.
5. The composite sheet for forming a protective film according to any one of claims 1 to 4, wherein the protective film-forming film has a transmittance of less than 20% for light having a wavelength of 800 nm.
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