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CN109075046B - Method for manufacturing semiconductor chip with protective film and method for manufacturing semiconductor device - Google Patents

Method for manufacturing semiconductor chip with protective film and method for manufacturing semiconductor device Download PDF

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Publication number
CN109075046B
CN109075046B CN201780025391.4A CN201780025391A CN109075046B CN 109075046 B CN109075046 B CN 109075046B CN 201780025391 A CN201780025391 A CN 201780025391A CN 109075046 B CN109075046 B CN 109075046B
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Prior art keywords
protective film
forming
film
meth
acrylate
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CN201780025391.4A
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CN109075046A (en
Inventor
稻男洋一
佐藤明德
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Lintec Corp
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Lintec Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the groups H01L21/18 - H01L21/326 or H10D48/04 - H10D48/07 e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • 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
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67092—Apparatus for mechanical treatment
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Dicing (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a method for manufacturing a semiconductor chip (19) with a protective film, wherein after a protective film (13) with energy ray solidification is attached to a semiconductor wafer (18), the protective film (13) is irradiated with energy rays to solidify, and then the semiconductor wafer (18) is cut. When the protective film (13 ') is produced by irradiating the protective film forming film (13) with energy rays, the tensile elastic modulus of the protective film (13') is 500MPa or more. The invention also relates to a method for manufacturing a semiconductor device, wherein a semiconductor chip (19) with a protective film is picked up and the semiconductor chip (19) is connected to a substrate.

Description

Method for manufacturing semiconductor chip with protective film and method for manufacturing semiconductor device
Technical Field
The present invention relates to a method for manufacturing a semiconductor chip with a protective film and a method for manufacturing a semiconductor device.
The present application claims priority based on japanese patent application No. 2016-92010 filed in japan, 4-28, and the content of which is incorporated herein.
Background
In recent years, a mounting method called a so-called flip-chip (face down) method has been applied to manufacture a semiconductor device. In the flip-chip method, a semiconductor chip having electrodes such as bumps on a circuit surface, the electrodes being bonded to a substrate, is used. Therefore, the back surface of the semiconductor chip opposite to the circuit surface may be exposed.
A resin film containing an organic material is formed as a protective film on the back surface of the exposed semiconductor chip, and the resin film is sometimes incorporated into a semiconductor device in the form of a semiconductor chip with a protective film.
The protective film is used to prevent cracks from occurring in the semiconductor chip after the dicing process and packaging.
For forming such a protective film, for example, a protective film forming composite sheet including a protective film forming film for forming a protective film on a support sheet is used. In the composite sheet for forming a protective film, the protective film can be formed by curing, and the support sheet can be used as a dicing sheet, so that the composite sheet for forming a protective film can be produced in which the protective film and the dicing sheet are integrated.
As such a composite sheet for forming a protective film, for example, a composite sheet for forming a protective film including a thermosetting film for forming a protective film, which is cured by heating, is mainly used at present. In this case, for example, a protective film is formed by attaching a protective film forming composite sheet to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer by a thermosetting protective film forming film, then curing the protective film forming film by heating, and then dividing the semiconductor wafer together with the protective film by dicing. Then, the semiconductor chip is directly separated from the support sheet in a state where the protective film is attached thereto, and picked up. The curing and cutting of the protective film forming film may be performed in the reverse order.
However, since the heat curing of the thermosetting protective film-forming film generally takes a long time of about several hours, it is desired to shorten the curing time. In view of the above, a film for forming a protective film, which can be cured by irradiation with energy rays such as ultraviolet rays, has been studied for forming a protective film. For example, disclose: an energy ray-curable protective film formed on the release film (see patent document 1); an energy ray-curable core-plate protective film capable of forming a protective film having high hardness and excellent adhesion to a semiconductor chip (see patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5144433
Patent document 2: japanese patent laid-open No. 2010-031183
Disclosure of Invention
Technical problem to be solved by the invention
However, in the manufacture of semiconductor chips and semiconductor devices using the energy ray-curable core protective films disclosed in patent documents 1 and 2, there is a concern that the dicing blade may be clogged and the protective layer may generate small chipping, that is, chipping, when dicing the semiconductor wafer.
In addition, the picked-up semiconductor chips with the protective film may be packaged in an embossed carrier tape 102 as shown in fig. 8 for use in the next step, and the embossed carrier tape 102 may be stored, transported, or subjected to commodity transaction in a state of being wound around a spool. When housed in the embossed carrier tape 102, the picked-up semiconductor chip 101 with the protective film is usually housed with the circuit surface side of the semiconductor chip facing the bottom of the pocket 102a of the embossed carrier tape 102 and the protective film side facing the opening of the pocket 102 a. An outer tape 103 constituting a cover portion of the embossed carrier tape 102 is attached, and the opening is closed to be packaged. When the semiconductor chip 101 with the protective film is used in the next step, for example, the embossed carrier tape 102 on which the semiconductor chip 101 with the protective film is packaged is set in a chip mounter together with a wire reel, and the semiconductor chip 101 with the protective film is mounted on a substrate. At this time, the outer tape 103 is peeled off, and the semiconductor chip 101 with the protective film is taken out from the pocket 102a of the embossed carrier tape 102, but the semiconductor chip 101 with the protective film may be attached to the outer tape 103 through the protective film, which may be an obstacle to the process of mounting the semiconductor chip 101 with the protective film on a substrate.
Accordingly, an object of the present invention is to provide a method for manufacturing a semiconductor chip with a protective film and a method for manufacturing a semiconductor device, the method for manufacturing a semiconductor chip with a protective film having the following characteristics: when dicing a semiconductor wafer, blade clogging and chipping are less likely to occur, and when accommodating a semiconductor chip with a protective film in a pocket of an embossed carrier tape, the adhesion of the semiconductor chip with the protective film to an external tape can be suppressed.
Technical means for solving the technical problems
In order to solve the above problems, in the method for manufacturing a semiconductor chip with a protective film according to the present invention, after attaching an energy-ray-curable film for forming a protective film to a semiconductor wafer, the film for forming a protective film is irradiated with energy rays to cure the film, and then the semiconductor wafer is diced, wherein when the film for forming a protective film is irradiated with energy rays to form a protective film, the tensile elastic modulus of the protective film is 500MPa or more.
In the method for manufacturing a semiconductor chip with a protective film according to the present invention, the protective film may be formed by irradiating the protective film-forming film with energy rays, then attaching the protective film to a support sheet, and then dicing the semiconductor wafer.
In the method for manufacturing a semiconductor chip with a protective film according to the present invention, the protective film forming film side of the protective film forming composite sheet including the protective film forming film on the support sheet may be attached to the semiconductor wafer.
The method for manufacturing a semiconductor device according to the present invention picks up a semiconductor chip with a protective film obtained by any one of the above manufacturing methods, and connects the semiconductor chip to a substrate.
Effects of the invention
According to the present invention, there is provided a method for manufacturing a semiconductor chip with a protective film, which is less likely to cause blade clogging and chipping when dicing a semiconductor wafer, and which can suppress the adhesion of the semiconductor chip with a protective film to an external sealing tape when accommodating the semiconductor chip with a protective film in a pocket of an embossed carrier tape, and a method for manufacturing a semiconductor device.
Drawings
Fig. 1 is a schematic view showing a method for manufacturing a semiconductor chip with a protective film according to the present invention.
Fig. 2 is a cross-sectional view schematically showing an embodiment of a composite sheet for forming a protective film which can be used in the present invention.
Fig. 3 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film which can be used in the present invention.
Fig. 4 is a cross-sectional view schematically showing still another embodiment of a composite sheet for forming a protective film which can be used in the present invention.
Fig. 5 is a cross-sectional view schematically showing still another embodiment of a composite sheet for forming a protective film which can be used in the present invention.
Fig. 6 is a cross-sectional view schematically showing still another embodiment of a composite sheet for forming a protective film which can be used in the present invention.
Fig. 7 is a cross-sectional view schematically showing an embodiment of a protective film-forming sheet that can be used in the present invention.
Fig. 8 is a cross-sectional view schematically showing a state in which a semiconductor chip with a protective film is accommodated in a pocket of an embossed carrier tape, and an outer tape is attached thereto to be covered, and a state after the outer tape is peeled off.
Detailed Description
(ii) semiconductor chip with protective film and method for manufacturing semiconductor device
Fig. 1 is a schematic view showing a method for manufacturing a semiconductor chip with a protective film according to the present invention.
In the method for manufacturing the semiconductor chip 19 with a protective film of the present invention, after the film 13 for forming the protective film curable with energy rays is attached to the semiconductor wafer 18, the film 13 for forming the protective film is irradiated with energy rays to be cured, and then the semiconductor wafer 18 is diced.
The protective film 13' is hard when the protective film forming film 13 is irradiated with energy rays and cured and then cut, so that blade clogging and chipping are less likely to occur when the semiconductor wafer 18 is cut. Further, since the protective film 13' has a tensile elastic modulus of 500MPa or more and is relatively hard, the semiconductor chip with the protective film can be prevented from adhering to the outer tape.
In the method for manufacturing a semiconductor chip with a protective film according to the present invention, the protective film may be formed by irradiating the protective film-forming film with energy rays, then attaching the protective film to a support sheet, and then dicing the semiconductor wafer. In this case, a product suitable for a semiconductor wafer, a protective film forming film to be manufactured, and a support sheet may be appropriately selected and used.
The method for manufacturing the semiconductor chip with a protective film of the present invention at this time is as follows: specifically, after attaching an energy ray-curable protective film forming film to the back surface (surface opposite to the electrode forming surface) of a semiconductor wafer, the protective film forming film is irradiated with energy rays and cured to form a protective film, and then the protective film is attached to a support sheet, and then the semiconductor wafer is diced.
In the method for manufacturing a semiconductor chip with a protective film according to the present invention, the protective film forming film side of the protective film forming composite sheet including the protective film forming film on the support sheet can be attached to the semiconductor wafer, whereby the attaching process can be simplified.
The method for manufacturing the semiconductor chip with a protective film of the present invention in this case can be as follows.
The method for manufacturing the semiconductor chip with the protective film of the invention comprises the following steps: that is, the composite sheet for forming a protective film, which is formed by providing the film for forming a protective film on the support sheet, is attached to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer by using the film for forming a protective film. Then, the protective film forming film is irradiated with energy rays to be cured, and then the semiconductor wafer is diced.
Next, the semiconductor chip with the protective film is directly separated from the supporting sheet in a state where the protective film is attached thereto by the same method as the conventional method, and the obtained semiconductor chip with the protective film is flip-chip connected to the circuit surface of the substrate, and then a semiconductor package is manufactured. Then, the target semiconductor device may be fabricated using the semiconductor package.
Composite sheet for forming protective film
The composite sheet for forming a protective film which can be used in the present invention is formed by providing an energy ray-curable protective film on a support sheet.
In the present specification, the "protective film forming film" refers to a protective film forming film before curing, and the "protective film" refers to a film obtained by curing a protective film forming film.
In the present invention, the "energy ray" refers to a ray having energy quanta in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, radiation rays, and electron beams.
The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, a black light lamp, an LED lamp, or the like as an ultraviolet source. The electron beam may irradiate an electron beam generated by an electron beam accelerator or the like.
In the present invention, "energy ray curability" refers to a property that is cured by irradiation with energy rays, and "non-energy ray curability" refers to a property that is not cured even if energy rays are irradiated.
In the present specification, a dicing target including a support sheet, an energy ray-curable protective film-forming film, and a semiconductor wafer in this order is referred to as a "laminate".
The adhesive force between the support sheet of the laminate and the protective film-forming film is not particularly limited, and may be 80mN/25mm or more, preferably 100mN/25mm or more, more preferably 150mN/25mm or more, and particularly preferably 200mN/25mm or more, for example. The upper limit is not particularly limited, and may be 10000mN/25mm or less, 8000mN/25mm or less, or 7000mN/25mm or less, for example. By adjusting the lower limit value or more, peeling of the protective film forming film and the supporting sheet at the time of dicing is suppressed, and scattering of the silicon chip at the time of dicing is suppressed, for example. Further, by adjusting the upper limit value or less, the adhesive force between the protective film and the support sheet when the protective film is formed by curing the protective film by irradiation with energy rays can be easily and appropriately adjusted.
In the present specification, the adhesive force between the support sheet and the protective film-forming film can be measured by a measurement method described later.
The protective film-forming film is cured by irradiation with energy rays, and becomes a protective film. The protective film protects the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer or the semiconductor chip. The protective film forming film is soft and can be easily attached to an object to be attached. When the protective film is formed by irradiating the protective film-forming film with energy rays, the adhesive force between the protective film and the support sheet is preferably 50 to 1500mN/25mm, more preferably 52 to 1450mN/25mm, and particularly preferably 53 to 1430mN/25mm.
When the adhesive force is equal to or higher than the lower limit, the picking-up of the semiconductor chip with the protective film outside the target is suppressed, and the semiconductor chip with the protective film can be picked up with high selectivity. When the adhesive force is equal to or lower than the upper limit, breakage and chipping of the semiconductor chip are suppressed when the semiconductor chip with the protective film is picked up. In this way, by setting the adhesive force within a specific range, the composite sheet for forming a protective film has good pickup adaptability.
In the present specification, the adhesive force between the protective film and the support sheet can be measured by a measurement method described later.
In one aspect of the present invention, the tensile elastic modulus of the protective film is preferably 500 to 10000MPa, more preferably 600 to 8000MPa, and particularly preferably 700 to 5000MPa.
By setting the tensile elastic modulus in such a range, blade clogging and chipping are less likely to occur when dicing a semiconductor wafer using the protective film, and the attachment of the protective film-attached semiconductor chip to the dicing tape can be suppressed when accommodating the protective film-attached semiconductor chip in the pocket of the embossed carrier tape.
In the present specification, the tensile elastic modulus can be measured by a measurement method described in examples described below.
In the composite sheet for forming a protective film which can be used in the present invention, by making the film for forming a protective film an energy ray-curable, the protective film can be formed by curing in a shorter time than in the case of the conventional composite sheet for forming a protective film having a thermosetting film for forming a protective film.
In the present invention, the protective film forming film and the support sheet described in the description of the protective film forming composite sheet can be used appropriately in the case where the protective film forming film and the support sheet are attached to the protective film forming film after attaching the protective film forming film to the back surface of the semiconductor wafer without using the protective film forming composite sheet.
In the present invention, the thickness of the semiconductor wafer or semiconductor chip to be used as the composite sheet for forming a protective film is not particularly limited, but is preferably 30 to 1000 μm, more preferably 100 to 300 μm, in order to obtain the effect of the present invention more remarkably.
The constitution of the present invention will be described in detail below.
Support sheet for very good
The support sheet may be formed of 1 layer (single layer) or may be formed of a plurality of layers of 2 or more layers. When the support sheet is composed of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.
In the present specification, the term "a plurality of layers may be identical to or different from each other" means "all layers may be identical to or different from each other, or only a part of layers may be identical to each other", and "a plurality of layers are different from each other" means "at least one of the constituent materials and thicknesses of each layer is different from each other".
Examples of the preferable support sheet include a support sheet in which an adhesive layer is laminated on a substrate in direct contact with the substrate, a support sheet in which an adhesive layer is laminated on a substrate via an intermediate layer, and a support sheet composed only of a substrate.
Hereinafter, examples of the composite sheet for forming a protective film which can be used in the present invention will be described for each type of such a supporting sheet with reference to the accompanying drawings. For the sake of easy understanding of the features of the present invention, the drawings used in the following description may be enlarged and show the portions that are the main portions, and the dimensional ratios of the respective constituent elements and the like are not necessarily the same as the actual ones.
Fig. 2 is a cross-sectional view schematically showing an embodiment of a composite sheet for forming a protective film which can be used in the present invention.
The protective film forming composite sheet 1A shown here is formed by providing an adhesive layer 12 on a base material 11, and providing a protective film forming film 13 on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, in other words, the composite sheet 1A for forming a protective film has a structure in which a film 13 for forming a protective film is laminated on one surface 10a of the support sheet 10. The protective film forming composite sheet 1A further includes a release film 15 on the protective film forming film 13.
In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one surface 11A of a base material 11, a film 13 for forming a protective film is laminated on the entire surface 12a of the adhesive layer 12, an adhesive layer 16 for a jig is laminated on a peripheral edge portion, which is a part of the surface 13a of the film 13 for forming a protective film, and a release film 15 is laminated on the surface 13a of the film 13 for forming a protective film, the surface of the adhesive layer 16 for a jig and the surface 16a (upper surface and side surface) of the adhesive layer 16 for a jig are not laminated.
In the protective film-forming composite sheet 1A, the adhesive force between the cured protective film-forming film 13 (i.e., the protective film 13 ') and the support sheet 10, in other words, the adhesive force between the protective film 13' and the adhesive layer 12 is preferably 50 to 1500mN/25mm.
The adhesive layer 16 for jigs may be, for example, an adhesive layer having a single-layer structure containing an adhesive component, or may be an adhesive layer having a plurality of layers in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material.
The composite sheet 1A for forming a protective film shown in fig. 2 is used by attaching the rear surface of a semiconductor wafer (not shown) to the front surface 13a of the film 13 for forming a protective film and further attaching the upper surface of the front surface 16a of the adhesive layer 16 for a jig to a jig such as a ring frame in a state where the release film 15 is removed.
Fig. 3 is a cross-sectional view schematically showing another embodiment of a composite sheet for forming a protective film which can be used in the present invention. In the drawings subsequent to fig. 3, the same components as those shown in the already described drawings are denoted by the same reference numerals as in the case of the already described drawings, and detailed description thereof is omitted.
The protective film forming composite sheet 1B shown here is the same as the protective film forming composite sheet 1A shown in fig. 2, except that the adhesive layer 16 for jigs is not provided. That is, in the composite sheet 1B for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the base material 11, the film 13 for forming a protective film is laminated on the entire surface 12a of the adhesive layer 12, and the release film 15 is laminated on the entire surface 13a of the film 13 for forming a protective film.
The composite sheet 1B for forming a protective film shown in fig. 3 is used by attaching the rear surface of a semiconductor wafer (not shown) to a partial region on the central side of the front surface 13a of the film 13 for forming a protective film in a state where the release film 15 is removed, and further attaching a region near the peripheral edge of the film 13 for forming a protective film to a jig such as a ring frame.
Fig. 4 is a cross-sectional view schematically showing still another embodiment of a composite sheet for forming a protective film which can be used in the present invention.
The protective film forming composite sheet 1C shown here is the same as the protective film forming composite sheet 1A shown in fig. 2 except that the adhesive layer 12 is not provided. That is, in the protective film forming composite sheet 1C, the support sheet 10 is composed of only the base material 11. A protective film forming film 13 is laminated on one surface 11a of the base material 11 (one surface 10a of the support sheet 10), a clamp adhesive layer 16 is laminated on a peripheral edge portion, which is a part of the surface 13a of the protective film forming film 13, and a release film 15 is laminated on the surface 13a of the protective film forming film 13, the surface on which the clamp adhesive layer 16 is not laminated and the surface 16a (upper surface and side surface) of the clamp adhesive layer 16.
In the composite sheet 1C for forming a protective film, the adhesive force between the film 13 for forming a protective film (i.e., protective film) and the support sheet 10 after curing, in other words, the adhesive force between the protective film and the substrate 11 is preferably 50 to 1500mN/25mm.
The composite sheet 1C for forming a protective film shown in fig. 4 is used by attaching the rear surface of a semiconductor wafer (not shown) to the front surface 13a of the film 13 for forming a protective film and further attaching the upper surface of the front surface 16a of the adhesive layer 16 for a jig to a jig such as a ring frame in the same manner as the composite sheet 1A for forming a protective film shown in fig. 2, with the release film 15 removed.
Fig. 5 is a cross-sectional view schematically showing still another embodiment of a composite sheet for forming a protective film which can be used in the present invention.
The protective film forming composite sheet 1D shown here is the same as the protective film forming composite sheet 1C shown in fig. 4, except that the adhesive layer 16 for jigs is not provided. That is, in the composite sheet 1D for forming a protective film, the protective film 13 for forming a protective film is laminated on one surface 11a of the base material 11, and the release film 15 is laminated on the entire surface 13a of the protective film 13 for forming a protective film.
The composite sheet 1D for forming a protective film shown in fig. 5 is used by attaching the rear surface of a semiconductor wafer (not shown) to a partial region on the center side of the front surface 13a of the film 13 for forming a protective film and further attaching a region near the peripheral edge of the film 13 for forming a protective film to a jig such as a ring frame in the same manner as the composite sheet 1B for forming a protective film shown in fig. 3, with the release film 15 removed.
Fig. 6 is a cross-sectional view schematically showing still another embodiment of a composite sheet for forming a protective film which can be used in the present invention.
The protective film forming composite sheet 1E shown here is the same as the protective film forming composite sheet 1B shown in fig. 3, except that the shape of the protective film forming film is different. That is, the composite sheet 1E for forming a protective film is formed by providing the adhesive layer 12 on the base material 11, and providing the protective film 23 on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, in other words, the protective film forming composite sheet 1E has a structure in which the protective film forming film 23 is laminated on one surface 10a of the support sheet 10. The protective film forming composite sheet 1E further includes a release film 15 on the protective film forming film 23.
In the composite sheet 1E for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the base material 11, and the protective film forming film 23 is laminated on a central side region which is a part of the surface 12a of the adhesive layer 12. The release film 15 is laminated on the surface 12a of the pressure-sensitive adhesive layer 12, on the surface 23a (upper surface and side surfaces) of the protective film 23 and on the surface where the protective film 23 is not laminated.
When the protective film forming composite sheet 1E is viewed from above, the surface area of the protective film forming film 23 is smaller than that of the adhesive layer 12, and has a circular shape, for example.
In the protective film-forming composite sheet 1E, the adhesive force between the cured protective film-forming film 23 (i.e., protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is preferably 50 to 1500mN/25mm.
The composite sheet 1E for forming a protective film shown in fig. 6 is used by attaching the back surface of a semiconductor wafer (not shown) to the front surface 23a of the film 23 for forming a protective film in a state where the release film 15 is removed, and further attaching the surface of the adhesive layer 12 on which the film 23 for forming a protective film is not laminated to a jig such as a ring frame.
In the composite sheet 1E for forming a protective film shown in fig. 6, an adhesive layer (not shown) for a surface-covering jig of the film 23 for forming a protective film may not be laminated on the surface 12a of the adhesive layer 12 as in the composite sheet for forming a protective film shown in fig. 2 and 4. Like the composite sheet for forming a protective film shown in fig. 2 and 4, the composite sheet for forming a protective film 1E including such an adhesive layer for a jig is used by attaching the surface of the adhesive layer for a jig to a jig such as a ring frame.
As described above, the composite sheet for forming a protective film which can be used in the present invention may be provided with an adhesive layer for a jig regardless of the form of the support sheet and the film for forming a protective film. However, as shown in fig. 2 and 4, a composite sheet for forming a protective film including a clamp adhesive layer on a film for forming a protective film is generally preferable.
The composite sheet for forming a protective film that can be used in the present invention is not limited to the composite sheet for forming a protective film shown in fig. 2 to 6, and a part of the structure of the composite sheet for forming a protective film shown in fig. 2 to 6 may be changed or deleted or another structure may be added to the composite sheet for forming a protective film described above, within a range that does not impair the effects of the present invention.
For example, in the composite sheet for forming a protective film shown in fig. 4 and 5, an intermediate layer may be provided between the base material 11 and the film 13 for forming a protective film. As the intermediate layer, an arbitrary intermediate layer may be selected according to the purpose.
In the composite sheet for forming a protective film shown in fig. 2, 3 and 6, an intermediate layer may be provided between the base material 11 and the adhesive layer 12. That is, in the composite sheet for forming a protective film which can be used in the present invention, the support sheet may be a support sheet in which a base material, an intermediate layer, and an adhesive layer are laminated in this order. Here, the intermediate layer is the same as the intermediate layer that can be provided in the protective film forming composite sheet shown in fig. 4 and 5.
In the composite sheet for forming a protective film shown in fig. 2 to 6, layers other than the intermediate layer may be provided at any position.
In the composite sheet for forming a protective film usable in the present invention, a part of the gap may be generated between the release film and the layer directly contacting the release film.
In the composite sheet for forming a protective film which can be used in the present invention, the size and shape of each layer can be arbitrarily adjusted according to the purpose.
In the composite sheet for forming a protective film which can be used in the present invention, as described later, it is preferable that a layer in the support sheet such as an adhesive layer which is in direct contact with the film for forming a protective film is non-energy ray curable. By using such a composite sheet for forming a protective film, a semiconductor chip having a protective film on the back surface can be more easily picked up.
The support sheet may be transparent, opaque, or colored for the purpose.
Among them, in the present invention in which the protective film forming film has energy ray curability, the support sheet is preferably a support sheet that transmits energy rays.
For example, the transmittance of light having a wavelength of 375nm in the support sheet is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, the curing degree of the protective film forming film is further improved when the protective film forming film is irradiated with energy rays (ultraviolet rays) through the support sheet.
On the other hand, the upper limit of the transmittance of light having a wavelength of 375nm in the support sheet is not particularly limited, and may be, for example, 95%.
In the support sheet, the transmittance of light having a wavelength of 532nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.
When the light transmittance is in such a range, printing can be performed more clearly when the protective film forming film or the protective film is irradiated with laser light through the support sheet to print the protective film.
On the other hand, the upper limit value of the transmittance of the support sheet for light having a wavelength of 532nm is not particularly limited, and may be, for example, 95%.
In the support sheet, the transmittance of light having a wavelength of 1064nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the light transmittance is in such a range, printing can be performed more clearly when the protective film forming film or the protective film is irradiated with laser light through the support sheet to print the protective film.
On the other hand, the upper limit value of the transmittance of light having a wavelength of 1064nm in the support sheet is not particularly limited, and may be, for example, 95%.
Next, each layer constituting the support sheet will be described in further detail.
Base material
The base material is in the form of a sheet or film, and examples of the constituent material thereof include various resins.
Examples of the resin include polyethylene such as Low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), and High Density Polyethylene (HDPE); polyolefin other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resin; ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-norbornene copolymers and other ethylene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins (resins obtained by using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers; a polystyrene; polycycloolefins; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2, 6-naphthalate, and wholly aromatic polyesters having an aromatic ring group in all the structural units; 2 or more copolymers of the above polyesters; poly (meth) acrylates; polyurethane; a urethane acrylate; polyimide; a polyamide; a polycarbonate; a fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyetherketone, and the like.
Examples of the resin include polymer alloys such as a mixture of the polyester and a resin other than the polyester. The polymer alloy of the above polyester and the resin other than the polyester is preferably a smaller amount of the resin other than the polyester.
Examples of the resin include crosslinked resins obtained by crosslinking 1 or 2 or more of the resins exemplified above; modified resins such as ionomers of 1 or 2 or more of the above resins exemplified above are used.
In the present specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to similar terms as (meth) acrylic acid.
The number of the resins constituting the base material may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
The substrate may be composed of 1 layer (single layer) or 2 or more layers, and in the case of being composed of a plurality of layers, the layers may be the same or different from each other, and the combination of the layers is not particularly limited.
The thickness of the base material is preferably 50 to 300. Mu.m, more preferably 60 to 100. Mu.m. By setting the thickness of the base material to such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor chip are further improved.
Here, "thickness of the substrate" refers to thickness of the entire substrate, and for example, thickness of the substrate composed of a plurality of layers refers to total thickness of all layers constituting the substrate.
In the present specification, "thickness" refers to a value expressed as an average value of 5 arbitrary parts of an object to be measured by a contact thickness meter.
The substrate is preferably a substrate having high thickness accuracy, that is, a substrate in which unevenness in thickness is suppressed regardless of the location. Among the above-mentioned constituent materials, examples of materials that can be used to construct such a substrate having high thickness accuracy include polyethylene, polyolefin other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, and the like.
The base material may contain, in addition to the main constituent materials such as the above resin, various known additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer).
The optical characteristics of the base material may be such that they satisfy the optical characteristics of the support sheet described above. That is, the substrate may be transparent, opaque, colored according to the purpose, or vapor deposited with other layers.
In the present invention in which the protective film forming film has energy ray curability, the substrate is preferably a substrate that transmits energy rays.
The substrate may be subjected to an oxidizing treatment such as a blast treatment, a solvent treatment, a corona discharge treatment, an electron beam irradiation treatment, a plasma treatment, an ozone-ultraviolet irradiation treatment, a flame treatment, a chromic acid treatment, a hot air treatment, or the like on the surface in order to improve adhesion to other layers such as an adhesive layer provided on the substrate.
The substrate may be a substrate having a surface subjected to a primer treatment.
When the antistatic coating layer is stacked and stored and the protective film-forming composite sheet is to be formed, the base material may be a base material having a layer or the like for preventing the base material from adhering to another sheet or the base material from adhering to the adsorption stage.
Among these, the substrate is particularly preferably subjected to electron beam irradiation treatment on the surface, from the viewpoint of suppressing chipping of the substrate due to blade friction at the time of cutting.
The substrate can be produced by a known method. For example, the resin-containing base material can be produced by molding a resin composition containing the above resin.
Adhesive layer
The adhesive layer is in the form of a sheet or film and contains an adhesive.
Examples of the binder include an adhesive resin such as an acrylic resin, a urethane resin, a rubber resin, a silicone resin, an epoxy resin, a polyvinyl ether, a polycarbonate, and an ester resin, and an acrylic resin is preferable.
In the present invention, the term "adhesive resin" is a concept including both a resin having adhesive properties and a resin having adhesive properties, and includes, for example, not only a resin having adhesive properties of the resin itself but also a resin exhibiting adhesive properties by being used together with other components such as additives, a resin exhibiting adhesive properties by the presence of an initiator such as heat or water, and the like.
The pressure-sensitive adhesive layer may be composed of 1 layer (single layer) or 2 or more layers, and in the case of being composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the pressure-sensitive adhesive layer is preferably 1 to 100. Mu.m, more preferably 1 to 60. Mu.m, particularly preferably 1 to 30. Mu.m.
Here, the "thickness of the adhesive layer" refers to the thickness of the entire adhesive layer, and for example, the thickness of the adhesive layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive layer.
The optical properties of the adhesive layer may be such that they satisfy the optical properties of the support sheet described above. That is, the adhesive layer may be transparent, opaque, or colored according to purposes.
In the present invention in which the protective film forming film has energy ray curability, the adhesive layer is preferably an adhesive layer that transmits energy rays.
The adhesive layer may be an adhesive layer formed using an energy ray-curable adhesive or an adhesive layer formed using a non-energy ray-curable adhesive. The adhesive layer formed using the energy ray-curable adhesive can easily adjust physical properties before and after curing.
Adhesive composition
The adhesive layer may be formed using an adhesive composition containing an adhesive. For example, the pressure-sensitive adhesive composition is applied to the surface of the pressure-sensitive adhesive layer to be formed, and if necessary, dried, whereby the pressure-sensitive adhesive layer can be formed at the target site. A more specific method of forming the adhesive layer is described in detail later together with a method of forming other layers. The content ratio of the components in the adhesive composition that do not vaporize at ordinary temperature is generally the same as the content ratio of the components in the adhesive layer. In the present specification, the term "normal temperature" refers to a temperature at which cooling or heating is not particularly performed, that is, a normal temperature, and examples thereof include 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 coating machines: air knife coater, doctor blade coater, bar coater, gravure coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, meyer bar coater, kiss coater, and the like.
The drying condition of the adhesive composition is not particularly limited, and when the adhesive composition contains a solvent described later, it is preferable to perform heat drying, and in this case, it is preferable to perform drying under conditions of, for example, 70 to 130 ℃ and 10 seconds to 5 minutes.
When the adhesive layer is energy ray-curable, examples of the adhesive composition containing an energy ray-curable adhesive agent include: an adhesive composition (I-1) comprising a non-energy ray-curable adhesive resin (I-1 a) (hereinafter, sometimes simply referred to 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-2 a) (hereinafter, sometimes simply referred to as "adhesive resin (I-2 a)") wherein an unsaturated group is introduced into a side chain of a non-energy ray-curable adhesive resin (I-1 a); an adhesive composition (I-3) comprising the adhesive resin (I-2 a) and an energy ray-curable compound.
< adhesive composition (I-1) >)
As described above, the adhesive composition (I-1) contains the non-energy ray-curable adhesive resin (I-1 a) and the energy ray-curable compound.
[ adhesive resin (I-1 a) ]
The adhesive resin (I-1 a) is preferably an acrylic resin.
Examples of the acrylic resin include acrylic polymers having at least a structural unit derived from an alkyl (meth) acrylate.
The structural units of the acrylic resin may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the alkyl group is preferably linear or branched.
Examples of alkyl (meth) acrylates 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 (also referred to as lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (also referred to as myristyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (also referred to as palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate, and nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like.
From the viewpoint of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth) acrylate having 4 or more carbon atoms in the alkyl group. The number of carbon atoms of the alkyl group is preferably 4 to 12, more preferably 4 to 8, from the viewpoint of further improving the adhesive force of the adhesive layer. The alkyl (meth) acrylate in which the alkyl group has 4 or more carbon atoms is preferably an alkyl acrylate.
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 the following monomers: the unsaturated group can be introduced into the side chain of the acrylic polymer by reacting the functional group with a crosslinking agent described later to form a starting point of crosslinking or by reacting the functional group with an unsaturated group in an unsaturated group-containing compound described later.
Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group.
That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, and the like.
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 (unsaturated alcohols having no (meth) acryl skeleton) such as vinyl alcohol and allyl alcohol.
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 the above-mentioned ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
The functional group-containing monomer is preferably a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.
The functional group-containing monomers constituting the acrylic polymer may be 1 or 2 or more, and in the case of 2 or more, 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, more preferably 2 to 32% by mass, and particularly preferably 3 to 30% by mass, based on the total mass of the structural unit.
The acrylic polymer may further have a structural unit derived from another monomer in addition to the structural unit derived from the alkyl (meth) acrylate and the structural unit derived from the functional group-containing monomer.
The other monomer is not particularly limited as long as it is a monomer copolymerizable with the alkyl (meth) acrylate and the like.
Examples of the other monomer include styrene, α -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.
The other monomers constituting the acrylic polymer may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
The acrylic polymer may be used as the non-energy ray-curable adhesive resin (I-1 a).
On the other hand, a compound obtained by reacting a functional group in the acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the energy ray curable adhesive resin (I-2 a).
The number of the adhesive resins (I-1 a) contained in the adhesive composition (I-1) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the adhesive resin (I-1 a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass, based on the total mass of the adhesive composition (I-1).
[ energy ray-curable Compound ]
The energy ray-curable compound contained in the adhesive composition (I-1) may be a monomer or oligomer having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Examples of 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) acrylates; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates, and the like.
Examples of the oligomer in the energy ray-curable compound include oligomers obtained by polymerizing the above-exemplified monomers.
The energy ray-curable compound is preferably urethane (meth) acrylate or urethane (meth) acrylate oligomer in view of having a large molecular weight and being less likely to reduce the storage elastic modulus of the adhesive layer.
The energy ray-curable compound contained in the adhesive composition (I-1) may be 1 or 2 or more, and in the case of 2 or more, 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, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass, based on the total mass of the adhesive composition (I-1).
[ Cross-linking agent ]
In the case of using the above-mentioned 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 as the adhesive resin (I-1 a), the adhesive composition (I-1) preferably further contains a crosslinking agent.
The crosslinking agent reacts with the functional group, for example, to crosslink the adhesive resins (I-1 a) with each other.
Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy-based crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine-based crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa [1- (2-methyl) -aziridinyl ] triphosphatriazine; metal chelate crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelates; isocyanurate-based crosslinking agents (crosslinking agents having an isocyanuric acid skeleton), and the like.
The crosslinking agent is preferably an isocyanate crosslinking agent in terms of improving the cohesive force of the adhesive and improving the adhesive force of the adhesive layer, and in terms of easy availability.
The crosslinking agent contained in the adhesive composition (I-1) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-1 a).
[ photopolymerization initiator ]
The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing the photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with an energy ray of a relatively low energy such as ultraviolet rays.
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 the like; acyl phosphine oxide compounds such as phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; alpha-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; a titanocene compound such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as diacetyl; benzil; a dibenzoyl group; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; 2-chloroanthraquinone, and the like.
As the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone can be used; amine and the like.
The photopolymerization initiator contained in the adhesive composition (I-1) may be 1 or 2 or more, and in the case of 2 or more, 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, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable compound.
[ other additives ]
The adhesive composition (I-1) may contain other additives than any of the above components within a range that does not impair 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 suppresses, for example, the crosslinking reaction outside the object in the adhesive composition (I-1) during storage due to the action of the catalyst mixed into the adhesive composition (I-1). Examples of the reaction retarder include compounds that form chelate complexes using chelates to the catalyst, and more specifically, compounds having 2 or more carbonyl groups (-C (=o) -) in 1 molecule.
The other additives contained in the adhesive composition (I-1) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the other additives is not particularly limited as long as it is appropriately selected according to the kind thereof.
[ solvent ]
The adhesive composition (I-1) may also contain a solvent. The adhesive composition (I-1) has improved coating adaptability to the surface to be coated by containing a solvent.
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 solvent may be used in the adhesive composition (I-1) without removing the solvent used in the production of the adhesive resin (I-1 a) from the adhesive resin (I-1 a), or may be added separately in the production of the adhesive composition (I-1) in the same type or in a different type from the solvent used in the production of the adhesive resin (I-1 a).
The solvent contained in the adhesive composition (I-1) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the solvent is not particularly limited, as long as it is appropriately adjusted.
< adhesive composition (I-2) >)
As described above, the adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2 a), and the adhesive resin (I-2 a) is obtained by introducing an unsaturated group into a side chain of the non-energy ray-curable adhesive resin (I-1 a).
[ adhesive resin (I-2 a) ]
The adhesive resin (I-2 a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1 a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.
The unsaturated group-containing compound is a compound having a group capable of bonding to the adhesive resin (I-1 a) by reacting with a functional group in the adhesive resin (I-1 a) 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 (also referred to as an ethylene group), an allyl group (also referred to as a 2-propenyl group), and the like, and a (meth) acryloyl group is preferable.
Examples of the group capable of bonding to the functional group in the adhesive resin (I-1 a) 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) acryloyloxyisocyanate, and glycidyl (meth) acrylate.
The number of the adhesive resins (I-2 a) contained in the adhesive composition (I-2) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2), the content of the adhesive resin (I-2 a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 10 to 90% by mass, based on the total mass of the adhesive composition (I-2).
[ Cross-linking agent ]
In the case of using the above-mentioned acrylic polymer having a structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1 a) as the adhesive resin (I-2 a), the adhesive composition (I-2) may further contain a crosslinking agent.
The crosslinking agent in the adhesive composition (I-2) may be the same as the crosslinking agent in the adhesive composition (I-1).
The crosslinking agent contained in the adhesive composition (I-2) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ photopolymerization initiator ]
The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing the photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with an energy ray of a relatively low energy such as ultraviolet rays.
The photopolymerization initiator in the adhesive composition (I-2) may be the same as the photopolymerization initiator in the adhesive composition (I-1).
The photopolymerization initiator contained in the adhesive composition (I-2) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ other additives ]
The adhesive composition (I-2) may contain other additives than any of the above components within a range that does not impair the effects of the present invention.
The other additives mentioned above in the adhesive composition (I-2) are the same additives as those in the adhesive composition (I-1).
The other additives contained in the adhesive composition (I-2) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2), the content of the other additives is not particularly limited as long as it is appropriately selected according to the kind thereof.
[ solvent ]
The adhesive composition (I-2) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
The solvent in the adhesive composition (I-2) may be the same as the solvent in the adhesive composition (I-1).
The solvent contained in the adhesive composition (I-2) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2), the content of the solvent is not particularly limited, as long as it is appropriately adjusted.
< adhesive composition (I-3) >)
As described above, the adhesive composition (I-3) contains the adhesive resin (I-2 a) and an energy ray-curable compound.
In the adhesive composition (I-3), the content of the adhesive resin (I-2 a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass, based on the total mass of the adhesive composition (I-3).
[ energy ray-curable Compound ]
The energy ray-curable compound contained in the adhesive composition (I-3) includes monomers and oligomers having an energy ray-polymerizable unsaturated group and being curable by irradiation with energy rays, and includes the same energy ray-curable compound as the energy ray-curable compound contained in the adhesive composition (I-1).
The energy ray-curable compound contained in the adhesive composition (I-3) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass, more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ photopolymerization initiator ]
The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing the photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with an energy ray of a relatively low energy such as ultraviolet rays.
The photopolymerization initiator in the adhesive composition (I-3) may be the same as the photopolymerization initiator in the adhesive composition (I-1).
The photopolymerization initiator contained in the adhesive composition (I-3) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total content of the adhesive resin (I-2 a) and the energy ray-curable compound.
[ other additives ]
The adhesive composition (I-3) may contain other additives than any of the above components within a range that does not impair the effects of the present invention.
The other additives mentioned above are the same as those in the adhesive composition (I-1).
The other additives contained in the adhesive composition (I-3) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-3), the content of the other additives is not particularly limited as long as it is appropriately selected according to the kind thereof.
[ solvent ]
The adhesive composition (I-3) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
The solvent in the adhesive composition (I-3) is the same as the solvent in the adhesive composition (I-1).
The solvent contained in the adhesive composition (I-3) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-3), the content of the solvent is not particularly limited as long as it is appropriately adjusted.
< adhesive composition other than adhesive compositions (I-1) to (I-3) >)
The adhesive composition (I-1), the adhesive composition (I-2) and the adhesive composition (I-3) are mainly described above, but the components described as the components contained in these components can be used in all the adhesive compositions other than these 3 adhesive compositions (in this specification, referred to as "adhesive compositions other than the adhesive compositions (I-1) to (I-3)").
The adhesive compositions other than the adhesive compositions (I-1) to (I-3) may be non-energy ray-curable adhesive compositions other than the energy ray-curable adhesive compositions.
Examples of the non-energy ray-curable adhesive composition include an adhesive composition (I-4) containing a non-energy ray-curable adhesive resin (I-1 a) such as an acrylic resin, a urethane resin, a rubber resin, a silicone resin, an epoxy resin, a polyvinyl ether, a polycarbonate, and an ester resin, and an adhesive composition containing an acrylic resin is preferable.
The adhesive compositions other than the adhesive compositions (I-1) to (I-3) preferably contain 1 or 2 or more crosslinking agents, and the content thereof may be the same as in the case of the adhesive composition (I-1) and the like.
< adhesive composition (I-4) >)
As a preferred adhesive composition among the adhesive compositions (I-4), for example, an adhesive composition containing the above-mentioned adhesive resin (I-1 a) and a crosslinking agent can be mentioned.
[ adhesive resin (I-1 a) ]
As the adhesive resin (I-1 a) in the adhesive composition (I-4), the same adhesive resin as the adhesive resin (I-1 a) in the adhesive composition (I-1) can be mentioned.
The number of the adhesive resins (I-1 a) contained in the adhesive composition (I-4) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-4), the content of the adhesive resin (I-1 a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass, based on the total mass of the adhesive composition (I-4).
[ Cross-linking agent ]
In the case of using the above-mentioned 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 as the adhesive resin (I-1 a), the adhesive composition (I-4) preferably further contains a crosslinking agent.
The crosslinking agent in the adhesive composition (I-4) may be the same compound as the crosslinking agent in the adhesive composition (I-1).
The crosslinking agent contained in the adhesive composition (I-4) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-1 a).
[ other additives ]
The adhesive composition (I-4) may contain other additives than any of the above components within a range that does not impair the effects of the present invention.
The other additives mentioned above are the same as those in the adhesive composition (I-1).
The other additives contained in the adhesive composition (I-4) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-4), the content of the other additives is not particularly limited as long as it is appropriately selected according to the kind thereof.
[ solvent ]
The adhesive composition (I-4) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
The solvent in the adhesive composition (I-4) is the same as the solvent in the adhesive composition (I-1).
The solvent contained in the adhesive composition (I-4) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-4), the content of the solvent is not particularly limited as long as it is appropriately adjusted.
In the composite sheet for forming a protective film which can be used in the present invention, the adhesive layer is preferably non-energy ray curable. This is because if the adhesive layer is energy ray curable, it may not be possible to suppress simultaneous curing of the adhesive layer when the protective film forming film is cured by irradiation of energy rays. If the adhesive layer and the protective film forming film are cured simultaneously, the cured protective film forming film and the adhesive layer may adhere to each other at the interface thereof to such an extent that they cannot be peeled off. In this case, it is difficult to peel the semiconductor chip having the protective film forming film after curing (hereinafter, sometimes referred to as "protective film-attached semiconductor chip") on the back surface from the support sheet having the adhesive layer after curing, and the protective film-attached semiconductor chip cannot be picked up normally. By making the adhesive layer in the support sheet of the present invention a non-energy ray curable adhesive layer, such a problem can be avoided with certainty, and the semiconductor chip with the protective film can be picked up more easily.
Here, the effect of the case where the pressure-sensitive adhesive layer is non-energy ray-curable is described, but even if the layer of the support sheet that is in direct contact with the protective film-forming film is a layer other than the pressure-sensitive adhesive layer, the same effect is exhibited as long as the layer is non-energy ray-curable.
Preparation method of adhesive composition
The adhesive compositions other than the adhesive compositions (I-1) to (I-3) such as the adhesive compositions (I-1) to (I-3) and the adhesive composition (I-4) are obtained by blending the above-mentioned adhesives and, if necessary, components other than the above-mentioned adhesives, etc. for constituting the adhesive composition.
The order of addition in blending the components is not particularly limited, and 2 or more components may be added simultaneously.
In the case of using a solvent, the solvent may be mixed with any of the blend components other than the solvent to dilute the blend components in advance, or the solvent may be mixed with any of the blend components without diluting the blend components other than the solvent in advance.
The method of mixing the components at the time of blending 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; and a method of mixing by applying ultrasonic waves.
The temperature and time at the time of adding and mixing the components are not particularly limited as long as the components to be blended are not deteriorated, and the temperature is preferably 15 to 30 ℃.
Sheet for forming protective film
In the present invention, the protective film forming film may be used in the form of a protective film forming sheet having a protective film forming film provided on a release film, or may be used by attaching a support sheet to the back surface of the semiconductor wafer.
The protective film forming film that can be used here is as described in the above-mentioned items of the protective film forming composite sheet.
Fig. 7 is a cross-sectional view schematically showing an embodiment of a protective film forming sheet 2F usable in the present invention.
The protective film forming sheet 2F shown here includes the protective film forming film 13 on the 1 st release film 15', and includes the 2 nd release film 15 "on the protective film forming film 13.
The protective film forming sheet 2F shown in fig. 7 is a sheet in which the rear surface of a semiconductor wafer (not shown) is attached to a partial region on the center side of the surface 13a of the protective film forming film 13 in a state where the 2 nd release film 15 "on the light release side is removed, and a support sheet is attached to the other surface 13b of the protective film forming film 13 on the opposite side to the surface 13a in a state where the 1 st release film 15' on the heavy release side is removed. Then, for example, as shown in fig. 4, the region near the peripheral edge portion of the protective film 13 is attached to a jig such as a ring frame via the adhesive layer 16 for jig, or, for example, as shown in fig. 6, the protective film forming sheet 2F is cut into a circular shape and laminated on a support sheet, and is held by the jig such as a ring frame by the adhesive portion of the support sheet.
Here, the release film having a small peeling force is referred to as a light-peeling-side release film, and the release film having a large peeling force is referred to as a heavy-peeling-side release film. If the peeling forces are different, the protective film forming film can be prevented from being lifted from the peeling film on the heavy peeling side when peeling only the peeling film on the light peeling side, or from being deformed by stretching so as to follow the two peeling films.
In the present invention, the adhesive force between the protective film and the support sheet obtained by curing the protective film-forming film is preferably 50 to 1500mN/25mm, more preferably 52 to 1450mN/25mm, particularly preferably 53 to 1430mN/25mm. When the adhesive force is equal to or higher than the lower limit, the picking-up of the semiconductor chip with the protective film outside the target is suppressed, and the semiconductor chip with the protective film can be picked up with high selectivity. When the adhesive force is equal to or lower than the upper limit, breakage and chipping of the semiconductor chip are suppressed when the semiconductor chip with the protective film is picked up. In this way, by setting the adhesive force within a specific range, the composite sheet for forming a protective film has good pickup adaptability.
In the present invention, even after the protective film forming film is cured, the laminated structure is referred to as "protective film forming composite sheet" as long as the laminated structure of the support sheet and the cured product of the protective film forming film (in other words, the support sheet and the protective film) is maintained.
The adhesion between the protective film and the support sheet can be measured by the following method.
That is, a protective film forming composite sheet having a width of 25mm and an arbitrary length is attached to an adherend through a protective film forming film of the protective film forming composite sheet.
Then, after the protective film forming film was cured by irradiation with energy rays to form a protective film, the support sheet was peeled off from the protective film attached to the adherend at a peeling speed of 300 mm/min. In this case, the peeling is so-called 180 ° peeling in which the support sheet is peeled in the longitudinal direction of the support sheet (the longitudinal direction of the composite sheet for forming the protective film) so that the surfaces of the protective film and the support sheet that are in contact with each other form an angle of 180 °. Then, the load (peel force) at 180℃peeling was measured, and the measured value was used as the adhesive force (mN/25 mm).
The length of the protective film-forming composite sheet to be measured is not particularly limited as long as the adhesive force can be stably detected, and is preferably 100 to 300mm. In the measurement, it is preferable to form a state in which the composite sheet for forming a protective film is attached to the adherend, and stabilize the attached state of the composite sheet for forming a protective film.
In the present invention, the adhesive force between the protective film forming film and the support sheet is not particularly limited, and may be, for example, 80mN/25mm or more, preferably 100mN/25mm or more, more preferably 150mN/25mm or more, and particularly preferably 200mN/25mm or more. When the adhesive force is set to 100mN/25mm or more, peeling of the protective film forming film from the support sheet is suppressed during dicing, and, for example, scattering of the semiconductor chip having the protective film forming film on the back surface from the support sheet is suppressed.
On the other hand, the upper limit of the adhesive force between the protective film-forming film and the support sheet is not particularly limited, and may be, for example, 4000mN/25mm, 3500mN/25mm, 3000mN/25mm, or the like. However, these are just one example.
The adhesive force between the protective film forming film and the support sheet can be measured by the same method as the adhesive force between the protective film and the support sheet described above, except that the protective film forming film to be measured is not cured by irradiation of energy rays.
The adhesive force between the protective film and the support sheet and the adhesive force between the protective film forming film and the support sheet can be appropriately adjusted by, for example, adjusting the kind and amount of the component contained in the protective film forming film, the constituent material of the layer in the support sheet on which the protective film forming film is provided, the surface state of the layer, and the like.
For example, the kind and amount of the component contained in the protective film-forming film can be adjusted by the kind and amount of the component contained in the protective film-forming composition described later. Further, by adjusting the type and content of the polymer (b) having no energy ray-curable group, the content of the filler (d), or the content of the crosslinking agent (f) among the components contained in the composition for forming a protective film, for example, the adhesive force between the protective film or the film for forming a protective film and the supporting sheet can be more easily adjusted.
For example, in the case where the layer of the support sheet on which the protective film forming film is provided is an adhesive layer, the constituent material thereof can be appropriately adjusted by adjusting the kind and amount of the component contained in the adhesive layer. The kind and amount of the component contained in the pressure-sensitive adhesive layer can be adjusted by the kind and amount of the component contained in the pressure-sensitive adhesive composition.
On the other hand, in the case where the layer provided with the protective film forming film in the support sheet is a base material, the adhesive force between the protective film or the protective film forming film and the support sheet can be adjusted by the surface state of the base material in addition to the adjustment by the constituent material of the base material. The surface state of the substrate may be, for example, subjected to a surface treatment as mentioned before as a treatment for improving adhesion between the substrate and other layers, that is, a concavity and convexity treatment by sand blasting, solvent treatment, or the like; oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment; the primer treatment or the like is carried out.
The protective film-forming film may be a film having an energy ray-curable property, for example, a film containing the energy ray-curable component (a).
The energy ray-curable component (a) is preferably uncured, preferably has adhesion, more preferably uncured and has adhesion.
The protective film may be formed of only 1 layer (single layer), or may be formed of a plurality of layers of 2 or more layers, and in the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the protective film-forming film is preferably 1 to 100. Mu.m, more preferably 5 to 75. Mu.m, particularly preferably 5 to 50. Mu.m. By setting the thickness of the protective film forming film to the above lower limit value or more, a protective film having higher protective ability can be formed. By setting the thickness of the protective film forming film to the above upper limit or less, the excessive thickness can be suppressed.
Here, 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 curing condition for curing the protective film forming film to form the protective film is not particularly limited as long as the protective film has a degree of curing sufficient to perform its function, and is appropriately selected according to the type of the protective film forming film.
For example, the illuminance of the energy ray at the time of curing the film for forming a protective film is preferably 4 to 280mW/cm 2 . The amount of energy rays at the time of curing is preferably 3 to 1000mJ/cm 2 。
Composition for Forming protective film
The protective film-forming film can be formed using a protective film-forming composition containing the constituent materials thereof. For example, the protective film-forming composition is coated on the surface of the protective film-forming film to be formed, and dried as necessary, whereby the protective film-forming film can be formed on the target portion. The content ratio of the components that do not vaporize at ordinary temperature in the composition for forming a protective film is generally the same as the content ratio of the above-mentioned components of the film for forming a protective film. Here, "normal temperature" is as described above.
The composition for forming a protective film may be applied by a known method, and examples thereof include the following methods using various coating machines: air knife coater, doctor blade coater, bar coater, gravure coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, meyer bar coater, kiss coater, and the like.
The drying condition of the composition for forming a protective film is not particularly limited, and when the composition for forming a protective film contains a solvent described later, it is preferable to perform heat drying, and in this case, it is preferable to perform drying under conditions of, for example, 70 to 130 ℃ and 10 seconds to 5 minutes.
< composition (IV-1) for Forming protective film >
Examples of the composition for forming a protective film include the composition (IV-1) for forming a protective film containing the energy ray-curable component (a).
[ energy ray-curable component (a) ]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays, and is also a component for imparting film-forming properties, flexibility, and the like to the film for forming a protective film.
Examples of the energy ray-curable component (a) include a polymer (a 1) having an energy ray-curable group and having a weight average molecular weight of 80000 ～ 2000000 and a compound (a 2) having an energy ray-curable group and having a molecular weight of 100 to 80000. The polymer (a 1) may be a polymer at least a part of which is crosslinked by a crosslinking agent (f) described later, or may be a polymer which is not crosslinked.
In the present specification, unless otherwise specified, the weight average molecular weight refers to a polystyrene equivalent measured by Gel Permeation Chromatography (GPC).
(Polymer (a 1) having an energy ray-curable group and having a weight-average molecular weight of 80000 ～ 2000000)
Examples of the polymer (a 1) having an energy ray-curable group and a weight average molecular weight of 80000 ～ 2000000 include an acrylic resin (a 1-1), wherein the acrylic resin (a 1-1) is obtained by polymerizing an acrylic polymer (a 11) and an energy ray-curable compound (a 12), wherein the acrylic polymer (a 11) has a functional group capable of reacting with a group of another compound, and the energy ray-curable compound (a 12) has a group reactive with the functional group and an energy ray-curable group such as 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 an amino group are substituted with groups other than hydrogen atoms), an epoxy group, and the like. However, the functional group is preferably a group other than a carboxyl group in view of preventing corrosion of circuits of a semiconductor wafer, a semiconductor chip, and the like.
Among these, the above functional group is preferably a hydroxyl group.
Acrylic Polymer having functional group (a 11)
Examples of the acrylic polymer (a 11) having the functional group include a polymer obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group, and a polymer obtained by copolymerizing a monomer other than the acrylic monomer (a non-acrylic monomer) in addition to these monomers.
The acrylic polymer (a 11) may be a random copolymer or a block copolymer.
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 (unsaturated alcohols having no (meth) acryl skeleton) such as vinyl alcohol and allyl alcohol.
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 the above-mentioned ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
The acrylic monomer having the above functional group is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.
The acrylic monomer having the functional group constituting the acrylic polymer (a 11) may be 1 or 2 or more, and in the case of 2 or more, 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 (also referred to as lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (also referred to as palmityl (meth) acrylate, heptadecyl (meth) acrylate), and alkyl (meth) acrylates having a chain structure in which the number of carbon atoms of the alkyl group constituting the alkyl ester is 1 to 18, such as octadecyl (meth) acrylate (also referred to as stearic (meth) acrylate).
Examples of the acrylic monomer having no functional group include alkoxyalkyl group-containing (meth) acrylates such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and the like; (meth) acrylic esters having an aromatic group, such as aryl (meth) acrylates including phenyl (meth) acrylate; non-crosslinking (meth) acrylamides and derivatives thereof; non-crosslinkable (meth) acrylic acid esters having tertiary amino groups such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
The acrylic monomer not having the functional group constituting the acrylic polymer (a 11) may be 1 or 2 or more, and in the case of 2 or more, 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 number of the non-acrylic monomers constituting the acrylic polymer (a 11) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer (a 11), the proportion (content) of the structural unit derived from the acrylic monomer having the functional group to the total mass of the structural units constituting the acrylic polymer (a 11) is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. By setting the ratio to such a range, the content of the energy ray-curable group in the acrylic resin (a 1-1) obtained by copolymerizing the acrylic polymer (a 11) and the energy ray-curable compound (a 12) can be easily adjusted to a preferable range in the curing degree of the 1 st protective film.
The acrylic polymer (a 11) constituting the acrylic resin (a 1-1) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
The content of the acrylic resin (a 1-1) in the composition (IV-1) for forming a protective film is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass, based on the total mass of the composition (IV-1) for forming a protective film.
Energy ray-curable Compound (a 12)
The energy ray-curable compound (a 12) preferably has 1 or 2 or more groups selected from the group consisting of isocyanate groups, epoxy groups and carboxyl groups as groups capable of reacting with the functional groups of the acrylic polymer (a 11), and more preferably has isocyanate groups as the groups. In the case where the energy ray-curable compound (a 12) has, for example, an isocyanate group as the group, the isocyanate group is likely to react with the hydroxyl group of the acrylic polymer (a 11) having a hydroxyl group as the functional group.
The energy ray-curable compound (a 12) preferably has 1 to 5 energy ray-curable groups per 1 molecule, more preferably 1 to 3 energy ray-curable groups.
Examples of the energy ray-curable compound (a 12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacrylyloxymethyl) ethyl isocyanate;
an acryl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
And acryl monoisocyanate compounds obtained by reacting a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
Among these, the energy ray-curable compound (a 12) is preferably 2-methacryloyloxyethyl isocyanate.
The energy ray-curable compound (a 12) constituting the acrylic resin (a 1-1) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the acrylic resin (a 1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a 12) to the content of the functional group derived from the acrylic polymer (a 11) 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 such a range, the adhesion of the protective film formed by curing becomes larger. In the case where the energy ray-curable compound (a 12) is a monofunctional (1 molecule having 1 group), the upper limit of the content ratio may be 100 mol%, but in the case where the energy ray-curable compound (a 12) is a polyfunctional (1 molecule having 2 or more groups), the upper limit of the content ratio may exceed 100 mol%.
The weight average molecular weight (Mw) of the polymer (a 1) is preferably 100000 ～ 2000000, more preferably 300000 ～ 1500000.
When at least a part of the polymer (a 1) is crosslinked by a crosslinking agent (f), the polymer (a 1) may be a polymer obtained by polymerizing a monomer having a group reactive with the crosslinking agent (f) other than any of the monomers described as monomers constituting the acrylic polymer (a 11), and crosslinking the polymer at a group reactive with the crosslinking agent (f), or may be a compound obtained by crosslinking a group reactive with the functional group derived from the energy ray-curable compound (a 12).
The polymer (a 1) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
(Compound (a 2) having an energy ray-curable group and having a molecular weight of 100 to 80000)
The energy ray-curable group included in the compound (a 2) having an energy ray-curable group and a molecular weight of 100 to 80000 includes a group containing an energy ray-curable double bond, and preferable examples thereof include a (meth) acryloyl group and a vinyl group.
The compound (a 2) is not particularly limited as long as the above conditions are satisfied, and examples thereof include low molecular weight compounds having an energy ray-curable group, epoxy resins having an energy ray-curable group, phenol resins having an energy ray-curable group, and the like.
Among the above-mentioned compounds (a 2), as the low molecular weight compound having an energy ray-curable group, for example, polyfunctional monomers or oligomers and the like are mentioned, and an acrylic compound having a (meth) acryloyl group is preferable.
As the above-mentioned acrylic acid ester compound, examples thereof include 2-hydroxy-3- (meth) acryloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloxypolyethoxy) phenyl ] propane, ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloxydiethoxy) phenyl ] propane, 9-bis [4- (2- (meth) acryloxyethoxy) phenyl ] fluorene, 2-bis [4- ((meth) acryloxypolypropoxy) phenyl ] propane, tricyclodecanedimethanol di (meth) acrylate (tricyclodecane dimethylol di (meth) acrylate), 1, 10-decane diol di (meth) acrylate, 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, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, difunctional (meth) acrylates such as 2, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1, 3-di (meth) acryloyloxypropane;
Polyfunctional (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) isocyanurate, epsilon-caprolactone-modified tris- (2- (meth) acryloyloxyethyl) isocyanurate, ethoxylated glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate;
multifunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers, and the like.
In the above-mentioned compound (a 2), as the epoxy resin having an energy ray-curable group or the phenol resin having an energy ray-curable group, for example, a resin described in paragraph 0043 or the like in "Japanese patent application laid-open No. 2013-194102" can be used. Such a resin is also a resin constituting the thermosetting component (h) described later, but is regarded as the above-mentioned compound (a 2) in the present invention.
The weight average molecular weight of the compound (a 2) is preferably 100 to 30000, more preferably 300 to 10000.
The number of the above-mentioned compounds (a 2) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
[ Polymer (b) having no energy ray-curable group ]
When the composition (IV-1) for forming a protective film and the film for forming a protective film contain the compound (a 2) as the energy ray-curable component (a), the composition preferably further contains a polymer (b) having no energy ray-curable group.
The polymer (b) may be a polymer at least a part of which is crosslinked by the crosslinking agent (f), or may be a polymer which is not crosslinked.
Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, polyester urethane resins, and the like.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter, may be simply referred to as "acrylic polymer (b-1)").
The acrylic polymer (b-1) may be a known polymer, for example, a homopolymer of 1 acrylic monomer, a copolymer of 2 or more acrylic monomers, or a copolymer of 1 or more acrylic monomers and 1 or 2 or more monomers other than acrylic monomers (non-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. Here, "substituted amino" is as previously described.
Examples of the alkyl (meth) acrylate 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 (also referred to as lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (also referred to as myristyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (also referred to as palmityl (meth) acrylate), heptadecyl (meth) acrylate, and alkyl (meth) acrylates having a chain structure in which the number of carbon atoms of the alkyl group constituting the alkyl ester is 1 to 18, such as octadecyl (meth) acrylate (also referred to as stearic (meth) acrylate).
Examples of the (meth) acrylic acid ester having a 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;
and cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate.
Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate.
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.
The polymer (b) which is crosslinked by the crosslinking agent (f) at least in part and does not have the energy ray-curable group is, for example, a polymer in which a reactive functional group in the polymer (b) reacts with the crosslinking agent (f).
The reactive functional group is not particularly limited as long as it is appropriately selected according to the kind of the crosslinking agent (f) and the like. For example, when the crosslinking agent (f) is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amino group, and the like, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. In the case where the crosslinking agent (f) is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amino group, an amide group, and the like, and among these, 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 in view of preventing corrosion of circuits of a semiconductor wafer and a semiconductor chip.
Examples of the polymer (b) having the reactive functional group and not having an energy ray-curable group include a polymer obtained by polymerizing at least a monomer having 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 or both of the acrylic monomer and the non-acrylic monomer mentioned above for the monomer constituting the acrylic polymer (b-1). Examples of the polymer (b) having a hydroxyl group as a reactive functional group include a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and in addition to the above, a polymer obtained by polymerizing a monomer in which 1 or 2 or more hydrogen atoms in the acrylic monomer or the non-acrylic monomer previously mentioned are substituted with the reactive functional group.
In the above polymer (b) having a reactive functional group, the proportion (content) of the amount of the structural unit derived from the monomer having a reactive functional group to the total mass of the structural units constituting the polymer (b) is preferably 1 to 25% by mass, more preferably 2 to 20% by mass. By setting the ratio to such a 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 ～ 2000000, more preferably 100000 ～ 1500000, from the viewpoint of better film-forming property of the composition (IV-1) for forming a protective film.
The number of the polymer (b) having no energy ray-curable group contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
The composition (IV-1) for forming a protective film includes a composition containing any one or both of the polymer (a 1) and the compound (a 2). When the protective film-forming composition (IV-1) contains the compound (a 2), it is preferable that the composition further contains the polymer (b) having no energy ray-curable group, and in this case, the composition further contains the compound (a 1). The composition (IV-1) for forming a protective film may not contain the compound (a 2) but may contain the polymer (a 1) and the polymer (b) having no energy ray-curable group.
When the protective film-forming composition (IV-1) contains the polymer (a 1), the compound (a 2), and the polymer (b) having no energy ray-curable group, the content of the compound (a 2) in the protective film-forming 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 (a 1) and the polymer (b) having no energy ray-curable group.
In the composition (IV-1) for forming a protective film, the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group (i.e., the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the film for forming a protective film) to the total content of components other than the solvent is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 15 to 70% by mass. When the ratio of the total content is in such a range, the energy ray curability of the protective film-forming film is further improved.
In the case where the composition (IV-1) for forming a protective film contains the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, the content of the polymer (b) is preferably 3 to 160 parts by mass, more preferably 6 to 130 parts by mass, relative to 100 parts by mass of the energy ray-curable component (a) in the composition (IV-1) for forming a protective film and the film for forming a protective film. By setting the content of the polymer (b) to such a range, the energy ray curability of the protective film-forming film becomes more excellent.
The composition (IV-1) for forming a protective film may contain, in addition to the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group, 1 or 2 or more kinds selected from the group consisting of a photopolymerization initiator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), a colorant (g), a thermosetting component (h), and a general-purpose additive (z), depending on the purpose. For example, by using the composition (IV-1) for forming a protective film containing the above-mentioned energy ray-curable component (a) and thermosetting component (h), the adhesion of the formed film for forming a protective film to an adherend is improved by heating, and the strength of the protective film formed from the film for forming a protective film is also improved.
[ photopolymerization initiator (c) ]
Examples of the photopolymerization initiator (c) 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 the like; acyl phosphine oxide compounds such as phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; alpha-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; a titanocene compound such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone compounds such as benzophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime); a peroxide compound; diketone compounds such as diacetyl; benzil; a dibenzoyl group; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; 2-chloroanthraquinone, and the like.
As the photopolymerization initiator (c), for example, quinone compounds such as 1-chloroanthraquinone can be used; amine and the like.
The photopolymerization initiator (c) contained in the protective film-forming composition (IV-1) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
When the photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the composition (IV-1) for forming a protective film is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable compound (a).
[ Filler (d) ]
The filling material (d) is contained in the protective film-forming film, so that the thermal expansion coefficient of the protective film obtained by curing the protective film-forming film can be easily adjusted, and the reliability of the package obtained by using the composite sheet for forming a protective film can be further improved by optimizing the thermal expansion coefficient with respect to the object to be formed of the protective film. By incorporating the filler (d) in the protective film-forming film, the moisture absorption rate of the protective film can be reduced or the heat dissipation property can be improved.
Examples of the filler (d) include a material made of a thermally conductive material.
The filler (d) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.
Examples of the preferable inorganic filler include powders of silica, alumina, talc, calcium carbonate, titanium white, red lead, 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 fiber, and the like.
Of these, the inorganic filler is preferably silica or alumina.
The average particle diameter of the filler (d) is not particularly limited, but is preferably 0.01 to 20. Mu.m, more preferably 0.1 to 15. Mu.m, particularly preferably 0.3 to 10. Mu.m. By setting the average particle diameter of the filler (d) to such a range, it is possible to suppress a decrease in light transmittance of the protective film while maintaining adhesion to the object on which the protective film is formed.
In the present specification, unless otherwise specified, the term "average particle diameter" refers to a particle diameter (D) at which the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method is 50% 50 ) Is a value of (2).
The number of filler (d) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
When the filler (d) is used, the content of the filler (d) (i.e., the content of the filler (d) of the protective film-forming film) in the protective film-forming composition (IV-1) is preferably 5 to 83% by mass, more preferably 7 to 78% by mass, based on the total content of all the components except the solvent. By setting the content of the filler (d) to such a range, the above-mentioned coefficient of thermal expansion can be more easily adjusted.
[ 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 the adhesiveness of the protective film forming film to an adherend can be improved. By using the coupling agent (e), the water resistance of the protective film obtained by curing the protective film-forming film is improved without impairing the heat resistance.
The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group of the energy ray-curable component (a), the polymer (b) having no energy ray-curable group, or the like, and more preferably a silane coupling agent.
Preferable examples of the silane coupling agent include 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3- (2-aminoethylamino) propyl methyl diethoxysilane, 3- (phenylamino) propyl trimethoxysilane, 3-anilinopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxy silane, and imidazole silane.
The number of the coupling agents (e) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, 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 protective film-forming composition (IV-1) and the protective film-forming film is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group. When the content of the coupling agent (e) is not less than the lower limit, the effect of using the coupling agent (e) such as an improvement in dispersibility of the filler (d) in the resin and an improvement in adhesion between the protective film-forming film and the adherend can be more remarkably obtained. By setting the content of the coupling agent (e) to the above upper limit value or less, the occurrence of outgassing can be further suppressed.
[ Cross-linking agent (f) ]
The initial adhesion and cohesion of the protective film-forming film can be adjusted by crosslinking the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group with the crosslinking agent (f).
Examples of the crosslinking agent (f) include an organic polyisocyanate compound, an organic polyimide 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.
Examples of the organic polyisocyanate compound include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compounds and the like"); a trimer, isocyanurate, or adduct of the aromatic polyisocyanate compound; and a terminal isocyanate urethane prepolymer obtained by reacting the aromatic polyisocyanate compound and the like with a polyol compound. The "adducts" are reactants of the aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound and low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, and examples thereof include xylylene diisocyanate adducts of trimethylolpropane as described below. "terminal isocyanate urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the terminal end of the molecule.
More specifically, examples of the organic polyisocyanate compound include 2, 4-toluene diisocyanate; 2, 6-toluene diisocyanate; 1, 3-xylylene diisocyanate; 1, 4-xylylene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4, 4' -diisocyanate; dicyclohexylmethane-2, 4' -diisocyanate; a compound obtained by adding 1 or 2 or more of toluene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate to all or a part of hydroxyl groups of a polyhydric alcohol such as trimethylolpropane; lysine diisocyanate, and the like.
Examples of the organic polyimine compound include N, N ' -diphenylmethane-4, 4' -bis (1-aziridinecarboxamide), trimethylolpropane-tris- β -aziridinyl propionate, tetramethylolmethane-tris- β -aziridinylpropionate, and N, N ' -toluene-2, 4-bis (1-aziridincarboxamide) triethylenemelamine.
When an organic polyisocyanate compound is used as the crosslinking agent (f), a hydroxyl-containing polymer is preferably used as the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group. When the crosslinking agent (f) has an isocyanate group and the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinking structure can be easily introduced into the film for forming a protective film by the reaction of the crosslinking agent (f) with the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group.
The crosslinking agent (f) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, 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 protective film-forming composition (IV-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 total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group. By setting the content of the crosslinking agent (f) to the lower limit value or more, the effect of using the crosslinking agent (f) can be more significantly obtained. By setting the content of the crosslinking agent (f) to the above upper limit value or less, the excessive use of the crosslinking agent (f) can be suppressed.
[ colorant (g) ]
Examples of the colorant (g) include known colorants such as inorganic pigments, organic pigments and organic dyes.
Examples of the organic pigment and organic dye include amine (amium) pigment, cyanine pigment, merocyanine pigment, croconium pigment, squaraine (croconium) pigment, squaraine (squaraine) pigment, azulene (azulenium) pigment, polymethine pigment, cai Kun pigment, pyran pigment, phthalocyanine pigment, cai Jing pigment, cai Naxian imine (nanolaminate) pigment, azo pigment, condensed azo pigment, indigo pigment, perinone (perinone) pigment, perylene pigment, dioxazine pigment, quinacridone pigment, isoindolinone pigment, quinophthalone pigment, pyrrole pigment, thioindigo pigment, metal complex pigment (metal complex dye), dithiol metal complex pigment, indophenol pigment, triallyl methane pigment, anthraquinone pigment, azone pigment, benzoquinone pigment, pyranone pigment, and naphthol pigment.
Examples of the inorganic pigment include carbon black, cobalt-based pigment, iron-based pigment, chromium-based pigment, titanium-based pigment, vanadium-based pigment, zirconium-based pigment, molybdenum-based pigment, ruthenium-based pigment, platinum-based pigment, ITO (indium tin oxide) based pigment, ATO (antimony tin oxide) based pigment, and the like.
The number of the coloring agents (g) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the case of using the colorant (g), the content of the colorant (g) in the protective film-forming film may be appropriately adjusted according to the purpose. For example, printing may be performed on the protective film by laser irradiation, and the printing visibility may be adjusted by adjusting the content of the colorant (g) in the protective film-forming film and adjusting the light transmittance of the protective film. In this case, in the composition (IV-1) for forming a protective film, the content of the colorant (g) (that is, the content of the colorant (g) in the film for forming a protective film) is preferably 0.1 to 10% by mass, more preferably 0.4 to 7.5% by mass, and particularly preferably 0.8 to 5% by mass, based on the total content of all components except the solvent. By setting the content of the colorant (g) to the lower limit value or more, the effect of using the colorant (g) can be more significantly obtained. By setting the content of the colorant (g) to the above upper limit value or less, excessive use of the colorant (g) can be suppressed.
[ thermosetting component (h) ]
The thermosetting component (h) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
Examples of the thermosetting component (h) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, and the like, and epoxy thermosetting resins are preferable.
(epoxy thermosetting resin)
The epoxy thermosetting resin is composed of an epoxy resin (h 1) and a thermosetting agent (h 2).
The epoxy thermosetting resin contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
Epoxy resin (h 1)
The epoxy resin (h 1) may be a known epoxy resin, for example, a multifunctional epoxy resin, a biphenyl compound, bisphenol a diglycidyl ether and its hydride, an o-cresol novolac epoxy resin, a dicyclopentadiene epoxy resin, a biphenyl epoxy resin, a bisphenol a epoxy resin, a bisphenol F epoxy resin, a phenylene skeleton epoxy resin, or the like.
As the epoxy resin (h 1), an epoxy resin having an unsaturated hydrocarbon group may also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, the reliability of the package obtained by using the composite sheet for forming a protective film is improved by using the epoxy resin having an unsaturated hydrocarbon group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of epoxy groups of a multifunctional epoxy resin into groups having an unsaturated hydrocarbon group. Such a compound is obtained, for example, by subjecting (meth) acrylic acid or a derivative thereof to an addition reaction with an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound 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 (also referred to as a vinyl group), a 2-propenyl group (also referred to as an allyl group), a (meth) acryl group, and a (meth) acrylamide group, and the like, and acryl is preferable.
The number average molecular weight of the epoxy resin (h 1) is not particularly limited, but is preferably 300 to 30000, more preferably 400 to 10000, particularly preferably 500 to 3000, from the viewpoints of curability of the film for forming a protective film, and strength and heat resistance of the protective film.
In the present specification, unless otherwise specified, the term "number average molecular weight" refers to a number average molecular weight measured by Gel Permeation Chromatography (GPC) and expressed as a value converted to standard polystyrene.
The epoxy equivalent of the epoxy resin (h 1) is preferably 100 to 1000g/eq, more preferably 150 to 800g/eq.
In the present specification, "epoxy equivalent" means the gram number (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be determined in accordance with JIS K7236: 2001.
The epoxy resin (h 1) may be used alone or in combination of 2 or more, and in the case of using 2 or more in combination, the combination and ratio thereof may be arbitrarily selected.
"Heat curing agent (h 2)
The thermosetting agent (h 2) functions as a curing agent for the epoxy resin (h 1).
Examples of the thermosetting agent (h 2) include compounds having 2 or more functional groups capable of reacting with an epoxy group in 1 molecule. Examples of the functional group include a group obtained by anhydrating a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group, and a group obtained by anhydrating a phenolic hydroxyl group, an amino group, and an acid group is preferable, and a phenolic hydroxyl group or an amino group is more preferable.
Examples of the phenolic curing agent having a phenolic hydroxyl group in the thermosetting agent (h 2) include polyfunctional phenol resins, biphenol, novolak phenol resins, dicyclopentadiene phenol resins, and aralkyl phenol resins.
Among the thermosetting agents (h 2), amine-based curing agents having an amino group include dicyandiamide (hereinafter, may be abbreviated as "dic") and the like.
The thermosetting agent (h 2) may also have an unsaturated hydrocarbon group.
Examples of the thermosetting agent (h 2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring of a phenol resin, and the like.
The unsaturated hydrocarbon group in the thermosetting agent (h 2) is the same as that in the epoxy resin having an unsaturated hydrocarbon group.
In the case of using a phenolic curing agent as the thermosetting agent (h 2), the thermosetting agent (h 2) is preferably a phenolic curing agent having a high softening point or glass transition temperature in view of improving the peelability of the protective film from the support sheet.
In the present specification, the "glass transition temperature" is expressed by measuring a DSC curve of a sample using a differential scanning calorimeter, and by expressing the temperature at the inflection point of the obtained DSC curve.
In the thermosetting agent (h 2), 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, an aralkyl phenol resin or the like is preferably 300 to 30000, more preferably 400 to 10000, particularly preferably 500 to 3000.
In the thermosetting agent (h 2), the molecular weight of the non-resin component such as biphenol and dicyandiamide is not particularly limited, and is preferably 60 to 500, for example.
The thermosetting agent (h 2) may be used alone or in combination of 2 or more, and in the case of using 2 or more in combination, the combination and ratio thereof may be arbitrarily selected.
When the thermosetting component (h) is used, the content of the thermosetting agent (h 2) in the protective film-forming composition (IV-1) and the protective film-forming film is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the epoxy resin (h 1).
When the thermosetting component (h) is used, the content of the thermosetting component (h) (for example, the total content of the epoxy resin (h 1) and the thermosetting agent (h 2)) in the protective film-forming composition (IV-1) and the protective film-forming film is preferably 1 to 500 parts by mass per 100 parts by mass of the content of the polymer (b) having no energy ray-curable group.
[ general additive (z) ]
The general-purpose additive (z) may be a known general-purpose additive, and may be arbitrarily selected according to the purpose, and is not particularly limited, and examples of preferable general-purpose additives include plasticizers, antistatic agents, antioxidants, getters, and the like.
The general-purpose additive (z) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
In the case of using the general-purpose additive (z), the content of the composition (IV-1) for forming a protective film and the general-purpose additive (z) for forming a protective film is not particularly limited, and may be appropriately selected according to the purpose.
[ solvent ]
The protective film-forming composition (IV-1) preferably further contains a solvent. The solvent-containing composition (IV-1) for forming a protective film is excellent in handleability.
The solvent is not particularly limited, and examples of the preferable solvent 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; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the protective film-forming composition (IV-1) may be 1 or 2 or more, and in the case of 2 or more, the combination and ratio thereof may be arbitrarily selected.
The solvent contained in the composition (IV-1) for forming a protective film is preferably methyl ethyl ketone, toluene, ethyl acetate, or the like, in view of more uniformly mixing the components contained in the composition (IV-1) for forming a protective film.
In one aspect of the present invention, a protective film forming film includes: the tricyclodecane dimethylol diacrylate as the energy ray-curable component (a 2) (content: 5 to 30 mass%, more preferably 8 to 25 mass% relative to the total mass of the solid components of the composition (IV-1) for forming a protective film); an acrylic resin (content: 12 to 32 mass%, more preferably 17 to 27 mass% relative to the total mass of the solid component of the composition (IV-1) for forming a protective film) composed of a structural unit derived from methyl acrylate (75 to 95 mass%, more preferably 80 to 90 mass% relative to the total mass of the acrylic resin), 2-hydroxyethyl acrylate (5 to 25 mass%, more preferably 10 to 20 mass% relative to the total mass of the acrylic resin), which is the polymer (b) having no energy ray-curable group; 1-hydroxy-cyclohexyl-phenyl-ketone (content: 0.1 to 1.1 mass%, more preferably 0.3 to 0.9 mass% relative to the total mass of the solid components of the protective film-forming composition (IV-1)) or 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-one (content: 0.1 to 1.1 mass%, more preferably 0.3 to 0.9 mass% relative to the total mass of the solid components of the protective film-forming composition (IV-1)) as the photopolymerization initiator (c); silica filler (content: 46 to 66 mass%, more preferably 51 to 61 mass% with respect to the total mass of the solid components of the composition (IV-1) for forming a protective film) as filler (d); 3-methacryloxypropyl trimethoxysilane (content: 0.1 to 0.7 mass%, more preferably 0.3 to 0.5 mass% relative to the total mass of the solid components of the composition (IV-1) for forming a protective film) as the coupling agent (e); and a pigment (content: 0.5 to 3.5 mass%, more preferably 1.0 to 3.0 mass% relative to the total mass of the solid components of the composition (IV-1) for forming a protective film) containing a phthalocyanine-based blue pigment, an isoindolinone-based yellow pigment, an anthraquinone-based red pigment, and a styrene acrylic resin as a colorant (g) (wherein the sum of the contents of the components does not exceed 100 mass% relative to the total mass of the solid components of the composition (IV-1)).
Preparation method of composition for Forming protective film
The composition for forming a protective film such as the composition (IV-1) for forming a protective film is obtained by blending the components for constituting the composition.
The order of addition in blending the components is not particularly limited, and 2 or more components may be added simultaneously.
In the case of using a solvent, the solvent may be mixed with any of the blend components other than the solvent to dilute the blend components in advance, or the solvent may be mixed with any of the blend components other than the solvent without diluting the blend components in advance.
The method of mixing the components at the time of blending 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; and a method of mixing by applying ultrasonic waves.
The temperature and time at the time of adding and mixing the components are not particularly limited as long as the components to be blended are not deteriorated, and the temperature is preferably 15 to 30 ℃.
As a composite sheet which is attached to the back surface of the semiconductor wafer or the semiconductor chip on the opposite side to the circuit surface and which has a layer exhibiting adhesiveness on the support sheet, there is a dicing die bonding sheet (dicing die bonding sheet) like the composite sheet for forming a protective film which can be used in the present invention.
However, the adhesive layer provided in the dicing die bonding sheet, after being picked up together with the semiconductor chip from the supporting sheet, functions as an adhesive for mounting the semiconductor chip on a substrate, a lead frame, or other semiconductor chips. On the other hand, the protective film forming film that can be used in the composite sheet for forming a protective film of the present invention is the same as the adhesive layer described above in terms of picking up the semiconductor chip together with the support sheet, but is finally cured to become a protective film, and has a function of protecting the back surface of the attached semiconductor chip. As described above, the film for forming a protective film of the present invention is different in use from the adhesive layer in the dicing die bonding sheet, and of course, also different in required performance. Reflecting the difference in the use, in general, the protective film forming film tends to be harder and difficult to pick up when compared with the adhesive layer in the dicing die bonding sheet. Therefore, it is generally difficult to directly transfer the adhesive layer in the dicing die bonding sheet as the protective film forming film in the protective film forming composite sheet. As the composite sheet for forming a protective film which can be used in the present invention and which has an energy ray-curable film for forming a protective film, a composite sheet for forming a protective film which is excellent in the suitability for picking up a semiconductor chip with a protective film can be suitably selected and used.
Method for producing composite sheet for forming protective film
The composite sheet for forming a protective film which can be used in the present invention can be produced by sequentially laminating the above layers in a corresponding positional relationship. The method of forming each layer is as described previously.
For example, in the case of laminating an adhesive layer on a substrate in the production of a support sheet, the adhesive composition may be applied to the substrate and dried as necessary.
On the other hand, for example, in the case where a protective film forming film is further laminated on an adhesive layer laminated on a substrate, the protective film forming composition may be applied on the adhesive layer to directly form the protective film forming film. The protective film may be formed by laminating a layer other than the protective film forming film on the pressure-sensitive adhesive layer by the same method using a composition for forming the layer. In this way, in the case of forming a continuous 2-layer laminated structure using any one of the compositions, the composition may be further applied on the layer formed of the above composition to newly form a layer.
Among these, the composition is preferably used to form a layer stacked later of these 2 layers on another release film, and the exposed surface of the formed layer on the opposite side to the side in contact with the release film is bonded to the exposed surface of the formed remaining layer, thereby forming a continuous 2-layer stacked 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.
For example, in the case of producing a protective film-forming composite sheet in which an adhesive layer is laminated on a substrate and a protective film-forming film is laminated on the adhesive layer (a protective film-forming composite sheet in which a support sheet is a laminate of a substrate and an adhesive layer), the protective film-forming film is formed on the release film by applying an adhesive composition on the substrate and drying it if necessary, thereby laminating an adhesive layer on the substrate in advance and additionally applying a protective film-forming composition on the release film and drying it if necessary. Then, the exposed surface of the protective film forming film is bonded to the exposed surface of the pressure-sensitive adhesive layer laminated on the substrate, and the protective film forming film is laminated on the pressure-sensitive adhesive layer, thereby obtaining a composite sheet for forming a protective film.
In the case of laminating the pressure-sensitive adhesive layer on the substrate, as described above, instead of the method of applying the pressure-sensitive adhesive composition on the substrate, the pressure-sensitive adhesive composition may be applied on the release film and dried as necessary, thereby forming the pressure-sensitive adhesive layer on the release film in advance, and the exposed surface of the layer may be bonded to one surface of the substrate, thereby laminating the pressure-sensitive adhesive layer on the substrate.
In either method, the release film may be removed at any timing after the formation of the target laminated structure.
In this way, since the layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of preliminarily forming the layers on the release film and bonding the layers to the surface of the target layer, the composite sheet for forming a protective film may be produced by appropriately selecting the layers in such a process as necessary.
The composite sheet for forming a protective film is usually 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 opposite side of the support sheet. Therefore, a composition for forming a layer constituting the outermost layer, such as a composition for forming a protective film, is applied to the release film (preferably, the release treated surface thereof), and dried as necessary, thereby forming a layer constituting the outermost layer in advance on the release film, and the remaining layers are laminated by any of the above methods on the exposed surface of the layer on the opposite side to the side in contact with the release film, and the protective film-forming composite sheet is obtained while the release film is not removed and bonded.
Method for using composite sheet for forming protective film
The protective film-forming composite sheet can be used, for example, by the following method.
That is, the protective film forming composite sheet is attached to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer with the protective film forming film. Then, the protective film is formed by irradiating the protective film-forming film with energy rays and curing the protective film-forming film. Next, the semiconductor wafer is divided along with the protective film by dicing to produce semiconductor chips. Then, the semiconductor chip is directly separated from the supporting sheet in a state where the protective film is attached (i.e., in the form of the semiconductor chip with the protective film) and picked up.
The picked-up semiconductor chip 101 with the protective film is accommodated in a pocket 102a of the embossed carrier tape 102 shown in fig. 8, and an outer tape 103 is attached to an opening of the pocket 102a, whereby the opening is sealed and packaged. Then, the embossed carrier tape 102 is stored, transported, or commodity-exchanged while being wound around a spool, and is used in a step of flip-chip bonding the semiconductor chip of the semiconductor chip 101 with the protective film to the circuit surface of the substrate in the next step.
In the present specification, the "embossed carrier tape" is a packaging material in which a plurality of recesses (sometimes referred to as pockets) are formed in a resin-made long sheet such as polystyrene, polyethylene terephthalate, or polypropylene at regular intervals, and the semiconductor chip with a protective film of the present invention can be accommodated in each of the plurality of pockets. The plurality of pockets are typically closed by: in a state where the object such as a semiconductor chip with a protective film of the present invention is accommodated, an elongated tape is attached to the opening. The embossed carrier tape of the semiconductor chip packaged with the protective film may be used in a state of being wound around a spool. For example, the above-described wire reel may be mounted on a chip mounter, and a semiconductor chip with a protective film may be mounted on a substrate. The pocket of the embossed carrier tape can be designed and processed according to the size of the object to be accommodated. Examples of the pockets of the embossed carrier tape in the present specification include pockets having a longitudinal dimension of 0.5mm to 30mm, a transverse dimension of 0.5mm to 30mm, and a depth of 0.1mm to 10 mm. The thickness of the strip-shaped outer sealing tape is 10-100 μm, and the strip-shaped outer sealing tape is formed by raw materials such as PET.
Next, the semiconductor chip with the protective film is directly separated from the supporting sheet in a state where the protective film is attached thereto by the same method as the conventional method, and the obtained semiconductor chip with the protective film is flip-chip connected to the circuit surface of the substrate, and then a semiconductor package is manufactured. Then, the target semiconductor device may be fabricated using the semiconductor package.
Examples
Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.
The components used in the preparation of the composition for forming a protective film are shown below.
Energy ray-curable component
(a2) -1: tricyclodecane dimethylol diacrylate (manufactured by Japanese chemical Co., ltd. "KAYARAD R-684", a difunctional ultraviolet curable compound, molecular weight 304).
Polymer without energy ray-curable group
(b) -2: acrylic resin (weight average molecular weight 300000) obtained by copolymerizing methyl acrylate (hereinafter, abbreviated as "MA") (85 parts by mass) and 2-hydroxyethyl acrylate (hereinafter, abbreviated as "HEA") (15 parts by mass)
Photopolymerization initiator
(c) -3: 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure (registered trademark) 184 manufactured by BASF corporation)
(c) -4:2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure (registered trademark) 379 manufactured by BASF corporation), molecular weight 380
Filling material
(d) -1: silica filler (fused silica filler, average particle size 8 μm)
Coupling agent
(e) -1: 3-methacryloxypropyl trimethoxysilane (manufactured by Xinyue chemical industry Co., ltd. "KBM-503", silane coupling agent)
Colorant(s)
(g) -1: a Pigment obtained by mixing 32 parts by mass of a phthalocyanine Blue Pigment (Pigment Blue 15:3), 18 parts by mass of an isoindolinone Yellow Pigment (Pigment Yellow 139) and 50 parts by mass of an anthraquinone Red Pigment (Pigment Red 177) and coloring the mixture so that the total amount of the 3 pigments/styrene acrylic resin amount=1/3 (mass ratio)
Example 1
< production of composite sheet for Forming protective film >
(preparation of composition for Forming protective film (IV-1))
The energy ray-curable component (a 2) -1, the polymer (b) -2, the photopolymerization initiator (c) -3, the photopolymerization initiator (c) -4, the filler (d) -1, the coupling agent (e) -1, and the colorant (g) -1 were dissolved or dispersed in methyl ethyl ketone so that the contents (solid content amounts, parts by mass) became the values shown in table 1, and stirred at 23 ℃, thereby preparing the protective film-forming composition (IV-1) having a solid content concentration of 50 mass%. Note that the "-" in the column containing the component in table 1 means that the composition (IV-1) for forming a protective film does not contain the component.
(preparation of adhesive composition (I-4))
A non-energy ray-curable adhesive composition (I-4) having a solid content concentration of 30 mass% was prepared, and the adhesive composition (I-4) contained an acrylic polymer (100 parts by mass, solid content) and a 3-functional xylylene diisocyanate-based crosslinking agent (10.7 parts by mass, solid content) ("Takenate D110N" manufactured by Sanjing Kagaku chemical Co., ltd.) and further contained methyl ethyl ketone as a solvent. The acrylic polymer was a polymer having a weight average molecular weight of 600000 obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter, abbreviated as "2 EHA") (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass).
(production of supporting sheet)
The pressure-sensitive adhesive composition (I-4) obtained above was applied to the release-treated surface of a release film (SP-PET 381031, thickness 38 μm, manufactured by Lindeke) having one surface of a polyethylene terephthalate film subjected to release treatment by silicone treatment, and the film was dried by heating at 120℃for 2 minutes, whereby a non-energy ray-curable pressure-sensitive adhesive layer having a thickness of 10 μm was formed.
Next, a polypropylene film (young's modulus 400, thickness 80 μm) as a base material was bonded to the exposed surface of the pressure-sensitive adhesive layer, thereby obtaining a support sheet (10) -1 having the pressure-sensitive adhesive layer on one surface of the base material.
(production of composite sheet for Forming protective film)
The composition (IV-1) for forming a protective film obtained above was applied to the release-treated surface of a release film (SP-PET 381031, thickness 38 μm, manufactured by Lindeke) obtained by releasing one surface of a polyethylene terephthalate film by silicone treatment using a doctor blade coater, and dried at 100℃for 2 minutes, thereby producing films (13) -9 for forming an energy ray-curable protective film having a thickness of 25. Mu.m.
Next, a release film was removed from the pressure-sensitive adhesive layer of the support sheet (10) -1 obtained as described above, and the exposed surface of the protective film-forming film (13) -9 obtained as described above was bonded to the exposed surface of the pressure-sensitive adhesive layer, to produce a protective film-forming composite sheet in which a base material, a pressure-sensitive adhesive layer, the protective film-forming film (13) -9, and a release film were laminated in this order in the thickness direction. The structure of the resulting composite sheet for forming a protective film is shown in table 2.
< evaluation of film for Forming protective film >
The tensile elastic modulus (Young's modulus) of the protective film-forming films (13) -9 was evaluated in the following manner.
Specifically, a protective film-forming sheet (thickness: 25 μm) was laminated in 2 layers to form a film having a thickness of 50 μm, and the sample was subjected to a tensile test (tensile speed: 50 mm/min) in a size of 15mm×100mm, and the tensile elastic modulus of the protective film-forming films (13) -9 was calculated from the slope of the stress-strain line at the initial stage of the stretching.
The evaluation results are shown in table 2.
< evaluation of protective film >
The tensile modulus (Young's modulus) after curing of the protective film-forming films (13) -9 was evaluated in the following manner.
That is, the protective film forming films (13) -9 (thickness: 25 μm) were laminated in 2 layers to form a film having a thickness of 50 μm, and UV (illuminance: 230 mW/cm) was irradiated 1 time from both sides 2 Light amount: 170mJ/cm 2 ) Curing it.
Then, the sample was subjected to a tensile test (tensile speed: 50 mm/min) in a size of 15mm X100 mm, and the tensile elastic modulus of the protective film was calculated from the slope of the stress-strain line at the initial stage of the stretching.
The evaluation results are shown in table 2.
(evaluation of cutting)
The composite sheet for forming a protective film obtained above was attached to a #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm) via the films (13) -9 for forming a protective film, and the sheet was further fixed to an annular frame and allowed to stand for 30 minutes.
Next, an ultraviolet irradiation apparatus (RAD 2000m/8 manufactured by Lindeke) was used at an illuminance of 195mW/cm 2 Light quantity 170mJ/cm 2 The protective film is produced by irradiating the protective film forming film (13) -9 with ultraviolet light from the support sheet (10) -1 side, thereby curing the protective film forming film (13) -9.
Next, the silicon wafer was diced together with the protective film using a dicing blade to obtain individual silicon chips of 2mm×2 mm.
Next, 20 silicon chips with protective films were picked up using a die bonder (die bonder) (a "bump-D02" manufactured by Canon Machinery). At this time, the cut surface of the silicon chip after dicing was observed by using a digital microscope (manufactured by Keyence Co., ltd., VHX-100, magnification: 100 times). If a crack or defect of 20 μm or more in width or depth is confirmed, the case where chips are generated is determined to be poor (B), and if such a defect is not confirmed, the case where chips are determined to be good (a). The results are shown in Table 2. The column "inhibition of chip cracking and chipping" in table 2 is written as the corresponding result.
(blade clogging evaluation)
The edge of the cut blade was observed with a digital microscope (manufactured by Keyence Co., ltd., VHX-100, magnification: 100 times), and the attached blade without a protective film was designated as "A", and the attached blade was designated as "B".
(evaluation of adhesion of outer seal tape)
The composite sheet for forming a protective film obtained above was attached to a #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm) by using the films (13) -9 for forming a protective film, and the sheet was further fixed to an annular frame and allowed to stand for 30 minutes.
Next, an ultraviolet irradiation apparatus (RAD 2000m/8 manufactured by Lindeke) was used at an illuminance of 195mW/cm 2 Light quantity 170mJ/cm 2 The protective film is produced by irradiating the protective film forming composite sheet with ultraviolet light from the support sheet (10) -1 side, thereby curing the protective film forming film (13) -9.
Then, the silicon wafer was diced together with the protective film using a dicing blade to obtain silicon chips having a thickness of the protective layer of 25 μm and a thickness of 350 μm in a vertical direction of 3mm×horizontal direction of 3mm and a thickness of the Si layer.
Next, 20 silicon chips with protective films were picked up using a die bonder (a "bump-D02" manufactured by Canon Machinery).
On an iron plate of 12cm in the longitudinal direction and 12cm in the transverse direction and 5mm in the thickness, 16 silicon chips with protective films obtained as described above were placed in a square lattice-like position of 4 pieces in the longitudinal direction and 4 pieces in the transverse direction, and an outer tape (manufactured by Sumitomo Bakelite Co., ltd., CSL-Z7302) of 12cm in the longitudinal direction and 3.8cm in the transverse direction was covered thereon, and the silicon chips with protective films were placed on a hot plate heated to 40℃and a metal plate was placed thereon, and the silicon chips with protective films were heated for one minute so that the pressure applied to the silicon chips with protective films became 350 gf. Then, the metal plate was removed, and the above-mentioned outer tape was peeled off, and whether or not the silicon chip with the protective film was attached to the outer tape was tested. The results are shown in Table 2.
As a determination method, it was determined that "B" was found when one of the 16 silicon chips with a protective film was attached to the outer tape, and "a" was found when one of the 16 silicon chips with a protective film was not attached to the outer tape.
< production and evaluation of protective film-forming sheet >
Example 2
The obtained composition (IV-1) for forming a protective film was applied to the release-treated surface of a 1 st release film (SP-PET 382150, thickness 38 μm, manufactured by Lindeke) obtained by releasing one surface of a polyethylene terephthalate film by silicone treatment by a doctor blade coater, and dried at 100℃for 2 minutes, thereby producing an energy ray-curable protective film forming film (13) -9) having a thickness of 25. Mu.m.
Next, a release surface of a 2 nd release film (SP-PET 381031, thickness 38 μm, manufactured by lindaceae) obtained by releasing a polyethylene terephthalate film on one surface by silicone treatment was bonded to the exposed surface of the obtained protective film forming film (13) -9, and a protective film forming sheet composed of a 1 st release film (1 st release film 15':25 μm in fig. 7) and a 2 nd release film 15″ was obtained.
After peeling the 2 nd release film of the protective film-forming sheet obtained above, the protective film-forming films (13) -9 obtained above were attached to a #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm), to obtain a laminate composed of the 6-inch silicon wafer, the protective film-forming films (13) -9, and the 1 st release film.
The 1 st release film was removed from the laminate obtained above, the release film was removed from the adhesive layer of the support sheet (10) -1 obtained in the same manner as in example 1, the protective film forming films (13) -9 and 1 st release film were attached to the exposed surface of the adhesive layer of the support sheet (10) -1, the protective film forming films (13) -9 were attached thereto, and the sheet was further fixed to the annular frame and allowed to stand for 30 minutes.
Next, an ultraviolet irradiation apparatus (RAD 2000m/8 manufactured by Lindeke) was used at an illuminance of 195mW/cm 2 Light quantity 170mJ/cm 2 The protective film is produced by irradiating the protective film forming composite sheet with ultraviolet light from the support sheet (10) -1 side, thereby curing the protective film forming film (13) -9.
Next, the silicon wafer was diced together with the protective film forming films (13) -9 using a dicing blade to obtain individual silicon chips of 2mm×2 mm.
The chip breakage and defect inhibition by dicing, the blade clogging inhibition and the adhesion to the tape were evaluated in the same manner as in example 1. The tensile elastic modulus was the same as in example 1. The evaluation results are shown in table 2.
Example 3
< production of composite sheet for Forming protective film >
(preparation of composition for Forming protective film (IV-1))
As shown in table 1, a composition (IV-1) for forming a protective film was prepared in the same manner as in example 1, except that the content (blending amount) of the energy ray-curable component (a 2) -1 was 10 parts by mass instead of 20 parts by mass, and the photopolymerization initiator (c) -4 was used instead of the photopolymerization initiator (c) -3, and the content (blending amount) of the photopolymerization initiator (c) -4 was 0.6 parts by mass.
(production of composite sheet for Forming protective film)
Using the protective film-forming composition (IV-1) obtained above, energy ray-curable protective film-forming films (13) -10 having a thickness of 25 μm were produced in the same manner as in example 1 except for this point.
A composite sheet for forming a protective film was produced in the same manner as in example 1, except that the protective film forming films (13) -10 were used instead of the protective film forming films (13) -9. The structure of the resulting composite sheet for forming a protective film is shown in table 2.
< production and evaluation of composite sheet for Forming protective film >
Using the composite sheet for forming a protective film obtained as described above, measurement of tensile modulus, evaluation of suppression of breakage and chipping of chips due to dicing, evaluation of suppression of blade clogging, and evaluation of adhesion to an encapsulation tape were performed by the same method as in example 1. The evaluation results are shown in table 2.
Comparative example 1
< production and evaluation of composite sheet for Forming protective film >
The composite sheet for forming a protective film obtained in the same manner as in example 1 was attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm) by using the films (13) -9 for forming a protective film, and the sheet was further fixed to an annular frame and allowed to stand for 30 minutes.
Next, the silicon wafer was diced together with the protective film forming films (13) -9 using a dicing blade to obtain individual silicon chips of 2mm×2 mm.
The chip breakage and defect inhibition by dicing, the blade clogging inhibition and the adhesion to the tape were evaluated in the same manner as in example 1. The tensile elastic modulus of the protective film-forming film at the time of cutting was the same as that of the protective film-forming film of example 1. The evaluation results are shown in table 2.
Comparative example 2
< production and evaluation of protective film-forming sheet >
A laminate composed of a 6-inch silicon wafer, protective film forming films (13) -9, and a 1 st release film was produced in the same manner as in example 2.
The 1 st release film was removed from the obtained laminate, the release film was removed from the adhesive layer of the support sheet (10) -1 obtained in the same manner as in example 1, the protective film forming films (13) -9 and 1 st release film were attached to the exposed surface of the adhesive layer of the support sheet (10) -1, the protective film forming films (13) -9 were attached thereto, the sheet was further fixed to the annular frame, and the sheet was allowed to stand for 30 minutes.
Next, the silicon wafer was diced together with the protective film forming films (13) -9 using a dicing blade to obtain individual silicon chips of 2mm×2 mm.
The chip breakage and defect inhibition by dicing, the blade clogging inhibition and the adhesion to the tape were evaluated in the same manner as in example 2. The tensile elastic modulus of the protective film-forming film at the time of cutting was the same as that of the protective film-forming film of example 2. The evaluation results are shown in table 2.
Comparative example 3
< production and evaluation of composite sheet for Forming protective film >
A composite sheet for forming a protective film was produced in the same manner as in example 3. The structure of the resulting composite sheet for forming a protective film is shown in table 2.
The composite sheet for forming a protective film obtained above was attached to a #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm) by using the films (13) -10 for forming a protective film, and the sheet was further fixed to an annular frame and allowed to stand for 30 minutes.
Next, the silicon wafer was diced together with the protective film forming films (13) -10 using a dicing blade to obtain individual silicon chips of 2mm×2 mm.
The chip breakage and defect inhibition by dicing, the blade clogging inhibition and the adhesion to the tape were evaluated in the same manner as in example 1. The tensile elastic modulus of the protective film-forming film at the time of cutting was the same as that of the protective film-forming film of example 3. The evaluation results are shown in table 2.
TABLE 1
TABLE 2
As is clear from the results of examples 1 to 3, when the semiconductor wafer is diced after the protective film forming film is cured by irradiation of energy rays, clogging of the dicing blade at the dicing is suppressed, and dicing suitability is also excellent. It is assumed that in examples 1 to 3, chipping of the protective film at the time of dicing can be suppressed and blade clogging can be suppressed by setting the tensile elastic modulus of the protective film at the time of dicing the semiconductor wafer to a high elastic modulus of 500MPa or more.
In contrast, in comparative examples 1 to 3, the semiconductor wafer was cut without irradiating the protective film forming film with energy rays to cure the film. At this time, since the tensile elastic modulus (young's modulus) of the protective film forming film at the time of dicing is 50 to 90MPa and is small, it is presumed that breakage or chipping of the chip due to dicing is generated, blade clogging is easily generated, and adhesion to the dicing tape is generated.
Industrial applicability
The present invention can be used for manufacturing a semiconductor device.
Description of the reference numerals
1A, 1B, 1C, 1D, 1E: a protective film-forming composite sheet;
2F: a protective film-forming sheet;
10: a support sheet;
10a: the surface of the support sheet;
11: a substrate;
11a: a surface of the substrate;
12: an adhesive layer;
12a: a surface of the adhesive layer;
13. 23: a protective film forming film;
13': a protective film;
13a, 23a: a surface (one surface) of the protective film forming film;
13b: a surface (other surface) of the protective film-forming film;
15: stripping the film;
15': 1 st release film;
15": a 2 nd release film;
16: an adhesive layer for a jig;
16a: the surface of the adhesive layer for the clamp;
17: an annular frame;
18: a semiconductor wafer;
19: a semiconductor chip;
20: a cutting blade;
21: an energy ray irradiation device;
101: a semiconductor chip with a protective film;
102: embossing the carrier tape;
102a: embossing the carrier tape pocket;
103: and (5) an outer sealing belt.

Claims (4)

1. A method for manufacturing a semiconductor chip with a protective film, wherein after attaching a film for forming the protective film with energy ray solidification to a semiconductor wafer, the film for forming the protective film is irradiated with energy ray to solidify, and then the semiconductor wafer is cut,
the protective film-forming film has the following characteristics:
irradiating the protective film forming film with illuminance 1 time from both sides of the protective film forming film: 230mW/cm 2 Light amount: 170mJ/cm 2 When the protective film is produced by UV of (2), the tensile elastic modulus of the protective film obtained by the following measurement method is 500MPa or more,
the measuring method comprises the following steps: the protective film of 15mm x 100mm was stretched at a stretching speed: a tensile test was conducted at 50mm/min, and the tensile elastic modulus was calculated from the slope of the stress-strain line at the initial stage of stretching.
2. The method of manufacturing a semiconductor chip with a protective film according to claim 1, wherein the protective film is formed by irradiating the protective film-forming film with energy rays, the protective film is attached to a support sheet, and then the semiconductor wafer is diced.
3. The method of manufacturing a semiconductor chip with a protective film according to claim 1, wherein the protective film forming film side of a protective film forming composite sheet including the protective film forming film on a support sheet is attached to the semiconductor wafer.
4. A manufacturing method of a semiconductor device, wherein a semiconductor chip with a protective film obtained by the manufacturing method according to any one of claims 1 to 3 is picked up, and the semiconductor chip is connected to a substrate.
CN201780025391.4A 2016-04-28 2017-04-25 Method for manufacturing semiconductor chip with protective film and method for manufacturing semiconductor device Active CN109075046B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
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