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CN109071845B - Film for forming protective film and composite sheet for forming protective film - Google Patents

Film for forming protective film and composite sheet for forming protective film Download PDF

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Publication number
CN109071845B
CN109071845B CN201780025032.9A CN201780025032A CN109071845B CN 109071845 B CN109071845 B CN 109071845B CN 201780025032 A CN201780025032 A CN 201780025032A CN 109071845 B CN109071845 B CN 109071845B
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China
Prior art keywords
protective film
forming
film
energy ray
meth
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CN201780025032.9A
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CN109071845A (en
Inventor
山本大辅
稻男洋一
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Lintec Corp
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Lintec Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • H01L21/18—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 the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The present invention provides a protective film forming film which is an energy ray curable protective film forming film, and when the protective film forming film is formed by irradiation of energy rays, the protective film forming film has the protective film according to JIS Z0237:2010 are determined at an inclination angle of 30 DEG, and the ball tack value is 2 or less.

Description

Film for forming protective film and composite sheet for forming protective film
Technical Field
The present invention relates to a protective film forming film and a protective film forming composite sheet.
The present application claims priority based on 28 days of 2016 in Japanese patent application 2016-092013, which was filed in Japan, and applies the content thereof.
Background
In recent years, a semiconductor device using a mounting method called a flip-chip (face down) method has been manufactured. 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 as a protective film is formed on the back surface of the exposed semiconductor chip, and the resin film may be incorporated into a semiconductor device as a semiconductor chip with a protective film.
To prevent cracks from being generated on the semiconductor chip after the dicing process or the packaging, a protective film is used.
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, in which the protective film forming film and the dicing sheet are integrated, can be produced.
As such a composite sheet for forming a protective film, for example, a composite sheet for forming a protective film having a thermosetting protective film which is cured by heating to form a protective film has been mainly used. In this case, for example, a composite sheet for forming a protective film is attached to the back surface (surface opposite to the electrode forming surface) of the semiconductor wafer by a thermosetting film for forming a protective film, and then the film for forming a protective film is cured by heating to form a protective film, and then the semiconductor wafer and the protective film are divided together by dicing to form semiconductor chips. After that, the semiconductor chip is picked up by separating it from the supporting sheet while maintaining the state where the protective film is attached. In addition, curing and cutting of the protective film forming film may be performed in the reverse order of the above.
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 this regard, 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, an energy ray-curable protective film formed on a release film (see patent document 1) and an energy ray-curable core protective film capable of forming a protective film having high hardness and excellent adhesion to a semiconductor chip (see patent document 2) have been disclosed.
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
In order to use the picked-up semiconductor chips with the protective film in the next step, the semiconductor chips may be packaged in an embossed carrier tape 102 as shown in fig. 7, and the embossed carrier tape 102 may be stored, transported, or transacted in a state of being wound into a reel. When the semiconductor chip 101 with the protective film after picking up is stored in the embossed carrier tape 102, the semiconductor chip is usually stored 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 102a, and the cover tape 103 constituting the cover part of the embossed carrier tape 102 is attached to close the opening to be packaged. When the semiconductor chip 101 with a protective film is used in the next process, for example, the embossed carrier tape 102 on which the semiconductor chip 101 with a protective film is packaged is set in a chip mounter together with a reel, and the semiconductor chip 101 with a protective film is mounted on a substrate. At this time, the cover 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 adhere to the cover tape 103 due to the protective film, and the step of mounting the semiconductor chip 101 with the protective film on the substrate may be hindered.
In view of the above, an object of the present invention is to provide a film for forming a protective film, which can form a protective film on the back surface of a semiconductor wafer or a semiconductor chip, and which has a characteristic of being able to suppress adhesion of the semiconductor chip with the protective film to a cover tape when the semiconductor chip with the protective film, which is cut and picked up, is stored in a pocket of an embossed carrier tape, and a composite sheet for forming a protective film, which includes the film for forming a protective film.
Technical means for solving the technical problems
In order to solve the above-described problems, the present invention provides a protective film forming film which is energy-ray-curable, and which, when irradiated with energy rays to form a protective film, is formed in accordance with JIS Z0237:2010 at an inclination angle of 30 DEG is 2 or less.
In the protective film-forming film of the present invention, the protective film-forming film preferably contains the energy ray-curable component (a).
In the protective film-forming film of the present invention, it is preferable that the protective film-forming film further contains a photopolymerization initiator (c).
In the film for forming a protective film of the present invention, the content of the photopolymerization initiator (c) is preferably 2.0 to 12.0 parts by mass per 100 parts by mass of the energy ray-curable component (a).
The present invention also provides a composite sheet for forming a protective film, which is formed by providing the protective film forming film described above on a support sheet.
That is, the present invention includes the following means.
[1] A protective film forming film which is an energy ray curable protective film forming film, wherein the protective film forming film has the protective film according to JIS Z0237 when the protective film is formed by irradiation of energy rays: 2010 are determined at an inclination angle of 30 DEG, and the ball tack value is 2 or less.
[2] The protective film-forming film according to [1], wherein the protective film-forming film contains an energy ray-curable component (a).
[3] The protective film-forming film according to [2], further comprising a photopolymerization initiator (c).
[4] The protective film-forming film according to [3], wherein the content of the photopolymerization initiator (c) is 2.0 to 12.0 parts by mass per 100 parts by mass of the energy ray-curable component (a).
[5] A composite sheet for forming a protective film comprising the film for forming a protective film of any one of [1] to [4] on a support sheet.
Effects of the invention
According to the present invention, it is possible to provide an energy ray-curable protective film forming film capable of suppressing adhesion of a semiconductor chip with a protective film to a cover tape when the semiconductor chip with the protective film is accommodated in a pocket of an embossed carrier tape, and a protective film forming composite sheet provided with the protective film forming film.
Drawings
Fig. 1 is a cross-sectional view schematically showing an embodiment of a protective film forming film according to the present invention.
Fig. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
Fig. 3 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
Fig. 4 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
Fig. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
Fig. 6 is a cross-sectional view schematically showing an embodiment of the protective film forming film of the present invention.
Fig. 7 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 a cover tape is attached to the semiconductor chip to cover the semiconductor chip, and a state in which the cover tape is peeled off.
Detailed Description
Film for forming protective film
The protective film forming film of the present invention is an energy-ray-curable protective film forming film, and when the protective film is formed by irradiating the protective film forming film with energy rays, the protective film is formed according to JIS Z0237:2010 are determined at an inclination angle of 30 DEG, and the ball tack value is 2 or less.
The protective film-forming film of the present invention may have a first release film on at least one surface, or may further have a second release film on the other surface. The protective film-forming film of the present invention can be provided in the form of a long film wound in a roll.
Fig. 1 is a cross-sectional view schematically showing an embodiment of a protective film forming film according to the present invention. In fig. 1, a first release film 15', a protective film forming film 13, and a second release film 15 "are laminated in this order.
In the present specification, the surface of the protective film forming film that is attached to the back surface of the semiconductor wafer (i.e., the surface opposite to the circuit surface) may be referred to as "surface (α)", and the surface opposite to the surface attached to the back surface of the semiconductor wafer may be referred to as "surface (β)".
When the protective film forming film of the present invention is irradiated with energy rays to form a protective film, at least one surface (β) of the protective film is formed according to JIS Z0237:2010 at an inclination angle of 30 DEG is 2 or less.
That is, as one side surface, the protective film forming film of the present invention is a protective film forming film having energy ray curability and used for forming a protective film on the back surface of a semiconductor wafer or a semiconductor chip, and preferably when the protective film forming film is irradiated with energy rays to form a protective film, the protective film has a surface (β) opposite to a surface (α) attached to the semiconductor wafer or the semiconductor chip side thereof, in accordance with JIS Z0237:2010 have a characteristic of a ball viscosity value of 0 to 2, measured at an inclination angle of 30 °, more preferably a characteristic of 0 to 2.
The composition of the protective film-forming film and the like will be described later.
The protective film-forming film of the present invention can be used as a protective film-forming film constituting a composite sheet for forming a protective film described later.
The protective film forming film and the base sheet can be used by attaching the protective film forming film to the back surface of the semiconductor wafer without using the protective film forming composite sheet, and then attaching the support sheet to the protective film forming film.
In the present invention, the protective film forming film may be used as a protective film forming sheet having a protective film forming film provided on a release film, as well as a composite sheet for forming a protective film described later, and may be used by attaching a support sheet to the back surface of the semiconductor wafer.
For example, fig. 1 is a cross-sectional view schematically showing an embodiment of a protective film forming sheet 2F using the protective film forming film of the present invention.
The protective film forming sheet 2F shown here includes the protective film forming film 13 on the first release film 15', and includes the second release film 15 "on the protective film forming film 13.
The protective film forming sheet 2F shown in fig. 1 is used in the following manner: the back surface of the semiconductor wafer (not shown) is attached to a part of the central side of the surface 13a of the protective film 13 (that is, the surface of the protective film 13 on the side having the second peeling film 15 ") in a state where the second peeling film 15" on the light peeling side is removed, and the base sheet is attached to the other surface 13b of the protective film 13 on the opposite side to the surface 13a in a state where the first peeling film 15' on the heavy peeling side is removed, and the region near the peripheral edge of the protective film 13 is attached to a jig such as a ring frame.
Here, the release film on the side having a small peeling force is referred to as a light-peeling-side release film, and the release film on the side 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 floating from the peeling film on the heavy peeling side when peeling only the peeling film on the light peeling side, and from being deformed by stretching in order to follow the two peeling films.
Composite sheet for forming protective film
The composite sheet for forming a protective film of the present invention is formed by providing an energy ray-curable protective film forming film on a support sheet.
In the present invention, the "protective film forming film" refers to a film before curing, and the "protective film" refers to a film obtained by curing a protective film forming film.
In the present specification, the term "energy ray" refers to a ray having energy 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 (fusion H lamp), a xenon lamp, a black light lamp, an LED lamp, or the like as an ultraviolet source. The electron beam can irradiate an electron beam generated by an electron beam accelerator or the like.
In the present specification, "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 when energy rays are irradiated.
The adhesion between the support sheet of the laminate and the protective film-forming film is not particularly limited, and may be, for example, 80mN/25mm or more, 100mN/25mm or more, 150mN/25mm or more, 200mN/25mm or more, or 10000mN/25mm or less, 8000mN/25mm or less, or 7000mN/25mm or less.
That is, the adhesion between the support sheet of the laminate and the protective film-forming film may be 80 to 10000mN/25mm, 150 to 8000mN/25mm, or 200 to 7000mN/25mm.
By adjusting the adhesion to the lower limit or more, scattering of the silicon chip during dicing can be suppressed, and penetration of cutting water between the protective film forming film and the supporting sheet can be prevented. Further, by adjusting the adhesion to the upper limit value or less, the adhesion between the protective film and the support sheet when the protective film is formed by curing by irradiation of energy rays can be easily and appropriately adjusted thereafter.
The protective film-forming film is cured by irradiation with energy rays, and becomes a protective film. The protective film is used to protect 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 adhesion 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 adhesion force is equal to or higher than the lower limit value, the pickup of the semiconductor chip with the protective film outside the target can be suppressed, and the semiconductor chip with the protective film as the target can be picked up with high selectivity. By setting the adhesion to the upper limit or less, breakage and chipping of the semiconductor chip can be suppressed when picking up the semiconductor chip with the protective film. In this way, by making the adhesion force within a specific range, the composite sheet for forming a protective film has good pickup suitability.
In the composite sheet for forming a protective film according to an embodiment of the present invention, the protective film can be formed by curing the protective film forming film in a shorter time than the conventional composite sheet for forming a protective film including the thermosetting protective film forming film by setting the protective film forming film to be energy ray-curable.
The thickness of the semiconductor wafer or semiconductor chip to be used as the composite sheet for forming a protective film of the present invention is not particularly limited, and is preferably 30 to 1000 μm, more preferably 100 to 300 μm, since the effect of the present invention can be more significantly obtained.
The constitution of the present invention will be described in detail below.
Support sheet for very good
The support sheet may be formed of one layer (single layer) or may be formed of a plurality of layers including two 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, "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 directly in contact with a substrate and is laminated thereon, 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, an example of the composite sheet for forming a protective film according to the present invention will be described for each type of such a supporting sheet with reference to the accompanying drawings. In order to facilitate understanding of the features of the present invention, important parts of the drawings used in the following description may be enlarged and displayed, and the dimensional ratios of the components and the like are not necessarily the same as those of the actual ones.
Fig. 2 is a cross-sectional view schematically showing an embodiment of the composite sheet for forming a protective film of the present invention.
The protective film forming composite sheet 1A shown here includes an adhesive layer 12 on a base material 11, and 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 the film 13 for forming a protective film is laminated on the surface 10a of one side of the support sheet 10 (for example, the surface of the support sheet 10 on the side of the adhesive layer 12). 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, the adhesive layer 12 is laminated on the surface 11A on one side of the base material 11, the protective film forming film 13 is laminated on the entire surface 12a of the adhesive layer 12 (that is, the surface of the adhesive layer 12 opposite to the side thereof in contact with the base material 11), the release film 15 is laminated on a part of the surface 13a of the protective film forming film 13 (that is, the surface of the protective film forming film 13 opposite to the side thereof in contact with the adhesive layer 12), that is, the region near the peripheral edge portion of the surface 13a, the surface of the protective film forming film 13a on which the adhesive layer 16 for a clamp is not laminated and the surface 16a (upper surface) of the adhesive layer 16 for a clamp, that is, the surface of the adhesive layer 16 for a clamp opposite to the side thereof in contact with the protective film forming film 13 and the side of the adhesive layer 16 for a clamp.
In the protective film-forming composite sheet 1A, the adhesion between the cured protective film-forming film 13 (i.e., protective film) and the support sheet 10, in other words, the adhesion between the protective film and the adhesive layer 12 is preferably 50 to 1500mN/25mm.
The pressure-sensitive adhesive layer 16 for jigs may have a single-layer structure containing a pressure-sensitive adhesive component, or may have a multilayer structure in which layers containing a pressure-sensitive adhesive component are laminated on both surfaces of a sheet as a core material.
The protective film forming composite sheet 1A shown in fig. 2 is used in the following manner: with the release film 15 removed, the back surface of the semiconductor wafer (not shown) is attached to the front surface 13a of the protective film forming film 13, and the upper surface of the front surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.
Fig. 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of 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 those in 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 jig adhesive layer 16 is not provided. That is, in the composite sheet 1B for forming a protective film, the adhesive layer 12 is laminated on the surface 11a of the substrate 11, the protective film 13 is laminated on the entire surface 12a of the adhesive layer 12 (that is, the surface of the adhesive layer 12 opposite to the surface thereof in contact with the substrate 11), and the release film 15 is laminated on the entire surface 13a of the protective film 13 (that is, the surface of the protective film 13 opposite to the surface thereof in contact with the adhesive layer 12).
The protective film forming composite sheet 1B shown in fig. 3 is used in the following manner: with the release film 15 removed, the rear surface of the semiconductor wafer (not shown) is attached to a partial region on the central side of the front surface 13a of the protective film 13, and the region near the peripheral edge of the protective film 13 is further attached to a jig such as a ring frame.
Fig. 4 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of 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. The protective film 13 is laminated on the surface 11a of the substrate 11 (the surface 10a of the support sheet 10), the adhesive layer 16 for jigs is laminated on a part of the surface 13a of the protective film 13 (that is, a surface of the protective film 13 opposite to the surface contacting the substrate 11), that is, a region near the peripheral edge of the surface 13a, and the release film 15 is laminated on the surface of the protective film 13, which is not laminated with the adhesive layer 16 for jigs, and the surface 16a (upper surface, that is, a surface of the adhesive layer 16 for jigs opposite to the surface contacting the protective film 13, and a surface of the adhesive layer 16 for jigs) of the surface 13a of the protective film 13.
In the composite sheet 1C for forming a protective film, the adhesion between the film 13 for forming a protective film (i.e., protective film) and the support sheet 10 after curing, in other words, the adhesion between the protective film and the substrate 11 is preferably 50 to 1500mN/25mm.
Like the protective film forming composite sheet 1A shown in fig. 2, the protective film forming composite sheet 1C shown in fig. 4 is used in the following manner: with the release film 15 removed, the back surface of the semiconductor wafer (not shown) is attached to the front surface 13a of the protective film forming film 13, and the upper surface of the front surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.
Fig. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of 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 jig adhesive layer 16 is not provided. That is, in the composite sheet 1D for forming a protective film, the protective film 13 is laminated on the surface 11a of one side of the base material 11, and the release film 15 is laminated on the entire surface 13a of the protective film 13 (that is, the surface of the protective film 13 opposite to the side thereof in contact with the base material 11).
Like the protective film forming composite sheet 1B shown in fig. 3, the protective film forming composite sheet 1D shown in fig. 5 is used in the following manner: with the release film 15 removed, the rear surface of the semiconductor wafer (not shown) is attached to a partial region on the central side of the front surface 13a of the protective film 13, and the region near the peripheral edge of the protective film 13 is further attached to a jig such as a ring frame.
Fig. 6 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
The protective film forming composite sheet 1E shown here is the same as the protective film forming composite sheet 1A shown in fig. 2 except that the shape of the protective film forming film is different. That is, the protective film forming composite sheet 1E includes the adhesive layer 12 on the base material 11, and the protective film forming 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 composite sheet 1E for forming a protective film has a structure in which a protective film forming film 23 is laminated on one surface 10a of the support sheet 10 (for example, the surface of the support sheet 10 on the side of the adhesive layer 12). The protective film forming composite sheet 1E further includes a release film 15 on the protective film forming film 23.
In the protective film forming composite sheet 1E, an adhesive layer 12 is laminated on the surface 11a of one side of the base material 11. A protective film forming film 23 is laminated on a part of the surface 12a of the adhesive layer 12 (i.e., the surface of the adhesive layer 12 opposite to the side thereof in contact with the substrate 11), that is, on the region on the center side of the surface 12 a. The release film 15 is laminated on the surface of the surface 12a of the adhesive layer 12, on which the protective film 23 is not laminated, and on the surface 23a of the protective film 23 (the upper surface, that is, the surface of the protective film 23 opposite to the side thereof in contact with the adhesive layer 12, and the side surface of the protective film 23).
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 adhesion between the cured protective film-forming film 23 (i.e., protective film) and the support sheet 10, in other words, the adhesion between the protective film and the adhesive layer 12 is preferably 50 to 1500mN/25mm.
The protective film forming composite sheet 1E shown in fig. 6 is used in the following manner: with the release film 15 removed, the back surface of the semiconductor wafer (not shown) is attached to the front surface 23a of the protective film forming film 23. Further, the surface of the adhesive layer 12 on which the protective film forming film 23 is not laminated is attached to a jig such as a ring frame.
In the protective film forming composite sheet 1E shown in fig. 6, an adhesive layer for a jig (not shown) may be laminated on the surface of the non-laminated protective film forming film 13 on the surface 12a of the adhesive layer 12 in the same manner as 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 provided with the adhesive layer for a jig as described above is used such that the surface of the adhesive layer for a jig is attached to a jig such as a ring frame.
As described above, the composite sheet for forming a protective film of the present invention may be provided with the adhesive layer for a jig, regardless of the form of the support sheet and the film for forming a protective film. As shown in fig. 2 and 4, the composite sheet for forming a protective film of the present invention having a pressure-sensitive adhesive layer for a jig is preferably provided with a pressure-sensitive adhesive layer for a jig on a film for forming a protective film.
The composite sheet for forming a protective film of the present invention is not limited to the composite sheet for forming a protective film shown in fig. 2 to 6, and a composite sheet for forming a protective film having a part of the composite sheet for forming a protective film shown in fig. 2 to 6 may be modified or deleted, or a composite sheet for forming a protective film having another structure may be further added to the composite sheet for forming a protective film described above, within a range not impairing 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 of the present invention, the support sheet may be formed by stacking the base material, the intermediate layer, and the adhesive layer in this order. Here, the intermediate layer means the same intermediate layer as that which can be provided in the protective film forming composite sheet shown in fig. 4 and 5.
The protective film-forming composite sheet shown in fig. 2 to 6 may be provided with a layer other than the intermediate layer at any position.
In the composite sheet for forming a protective film of the present invention, a part of the gap may be generated between the release film and the layer in direct contact with the release film.
In the composite sheet for forming a protective film of 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 of the present invention, as described later, it is preferable that the layer of the support sheet that is in direct contact with the film for forming a protective film, such as the adhesive layer, is non-energy ray curable. The composite sheet for forming the protective film can pick up the semiconductor chip with the protective film on the back surface more easily.
The support sheet may be transparent or opaque, or may be colored according to the purpose.
Among them, in the present invention in which the protective film forming film has energy ray curability, it is preferable that the support sheet 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 by irradiation of the protective film forming film 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%.
That is, the transmittance of light having a wavelength of 375nm in the support sheet is preferably 30 to 95%, more preferably 50 to 95%, and particularly preferably 70 to 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, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and printing is performed thereon, the printing can be performed more clearly.
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%.
That is, the light transmittance of the support sheet at 532nm is preferably 30 to 95%, more preferably 50 to 95%, and particularly preferably 70 to 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, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and printing is performed thereon, the printing can be performed more clearly.
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%.
That is, the transmittance of light having a wavelength of 1064nm in the support sheet is preferably 30 to 95%, more preferably 50 to 95%, and particularly preferably 70 to 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 (sometimes abbreviated as LDPE), linear low density polyethylene (sometimes abbreviated as LLDPE), and high density polyethylene (sometimes abbreviated as HDPE); polyolefins 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 each having an aromatic ring group in its constituent unit; copolymers of two or more of the 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.
The resin may be, for example, a polymer alloy such as a mixture of the polyester and a resin other than the polyester. Preferably, the amount of resin other than polyester in the polymer alloy of the polyester and resin other than polyester is a small amount.
Examples of the resin include crosslinked resins obtained by crosslinking one or more of the above resins; modified resins such as ionomers of one or two 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". Similar terms to (meth) acrylic acid are also the same.
The resin constituting the base material may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The substrate may be composed of one layer (single layer) or two or more layers, and when the substrate is 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 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 can be further improved.
Here, "thickness of the substrate" refers to thickness of the entire substrate, 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 thicknesses measured at arbitrary five positions by a contact thickness meter.
The substrate is preferably a substrate having high thickness accuracy, that is, a substrate in which variation in thickness is suppressed at any position. Examples of the material that can be used as the material constituting the base material having such high thickness accuracy include polyethylene, polyolefin other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymer.
The base material may contain, in addition to the main constituent materials such as the 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 or opaque, may be colored according to the purpose, or may be vapor-deposited with another layer.
In the present invention in which the protective film forming film has energy ray curability, it is preferable that the base material transmits energy rays.
In order to improve the adhesion to other layers such as an adhesive layer provided thereon, the substrate may be one having been subjected to an oxidizing treatment such as a blast treatment, a solvent treatment, a surface roughening 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.
In addition, the substrate may be a substrate whose surface is treated with a primer.
In addition, when the antistatic coating layer and the protective film-forming composite sheet are laminated and stored, the substrate may have a layer or the like for preventing the adhesion of the substrate to another sheet or the adhesion of the substrate to a suction table.
Among them, from the viewpoint of suppressing the occurrence of a broken piece of the substrate due to the friction of the blade at the time of cutting, it is particularly preferable that the substrate is a substrate whose surface is subjected to the electron beam irradiation treatment.
The substrate can be produced by a known method. For example, a resin-containing substrate can be produced by molding a resin composition containing the resin.
Adhesive layer
The adhesive layer is in the form of a sheet or film and contains an adhesive.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferable.
In the present specification, the term "adhesive resin" is a concept including both a resin having an adhesive property and a resin having an adhesive property. For example, the resin includes not only a resin having adhesiveness itself but also a resin exhibiting adhesiveness by use together with other components such as an additive, or a resin exhibiting adhesiveness by the presence of a trigger (trigger) such as heat or water.
The adhesive layer may be formed of one layer (single layer) or two or more layers, and when the adhesive layer is formed 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 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 or opaque, or may be colored according to the purpose.
In the present invention in which the protective film forming film has energy ray curability, it is preferable that the adhesive layer transmits energy rays.
The adhesive layer may be formed using an energy ray-curable adhesive or a non-energy ray-curable adhesive. The adhesive layer formed by using the energy ray-curable adhesive can easily adjust physical properties before and after curing.
Adhesive agent composition >
The adhesive layer can be formed from an adhesive composition containing an adhesive. For example, the adhesive composition is applied to the surface of the adhesive layer to be formed and dried as necessary, whereby the adhesive layer can be formed at the target site. A more specific method of forming the adhesive layer will be described in detail later together with a method of forming other layers. The content ratio of the components in the adhesive composition, which are not gasified at normal 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 adhesive composition may be applied by a known method, and examples thereof include various coating machines such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll knife coater, a curtain coater, a die coater, a blade coater, a screen coater (screen coater), a meyer bar coater, and a kiss coater.
The drying condition of the adhesive composition is not particularly limited, but 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 ℃ for 10 seconds to 5 minutes.
When the adhesive layer is energy ray-curable, examples of the adhesive composition containing an energy ray-curable adhesive, that is, the adhesive composition that is energy ray-curable, include: an adhesive composition (I-1) comprising a non-energy ray-curable adhesive resin (I-1 a) (hereinafter, sometimes abbreviated as "adhesive resin (I-1 a)") and an energy ray-curable compound; an adhesive composition (I-2) comprising an energy ray-curable adhesive resin (I-2 a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2 a)") having an unsaturated group introduced into a side chain of the non-energy ray-curable adhesive resin (I-1 a); an adhesive composition (I-3) containing 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) ]
Preferably, the adhesive resin (I-1 a) is 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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the present specification, "derived from" means that the chemical structure is changed for polymerization.
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.
More specifically, 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 stearyl (meth) acrylate may be referred to as stearic acid, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like.
From the point of improving the adhesive force of the adhesive layer, it is preferable that the acrylic polymer 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 point of further improving the adhesive force of the adhesive layer. Further, 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 a starting point of crosslinking by a reaction between the functional group and a crosslinking agent described later, and a functional group-containing monomer in which an unsaturated group is introduced into a side chain of an acrylic polymer by a reaction between the functional group and 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 such as vinyl alcohol and allyl alcohol (i.e., unsaturated alcohols having no (meth) acryl skeleton).
Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (i.e., 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 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 monomer constituting the acrylic polymer may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic 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, relative to the total amount of the structural units constituting the acrylic polymer.
The acrylic polymer may further have a structural unit derived from another monomer in addition to a structural unit derived from an alkyl (meth) acrylate.
The other monomer is not particularly limited as long as it is a monomer copolymerizable with the alkyl (meth) acrylate or 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 one or two or more, and when two or more are used, the combination and ratio thereof may be arbitrarily selected.
The acrylic polymer can be used as the above-mentioned non-energy ray-curable adhesive resin (I-1 a).
On the other hand, a substance produced by reacting an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group (also referred to as an energy ray-polymerizable group) with a functional group in the acrylic polymer can be used as the energy ray-curable adhesive resin (I-2 a) described above.
In the present specification, "energy ray polymerizability" refers to a property of polymerization by irradiation with energy rays.
The adhesive resin (I-1 a) contained in the adhesive composition (I-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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, relative to 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) includes a monomer or oligomer having an energy ray-polymerizable unsaturated group and curable by irradiation with energy rays.
Examples of the monomer in the energy ray-curable compound include polyvalent (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol (meth) acrylate; urethane (meth) 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 monomers exemplified above.
The energy ray-curable compound is preferably urethane (meth) acrylate or urethane (meth) acrylate oligomer in terms of having a large molecular weight and not easily lowering the storage modulus of the adhesive layer.
The energy ray-curable compound contained in the adhesive composition (I-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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, relative to the total mass of the adhesive composition (I-1).
[ Cross-linking agent ]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1 a), it is preferable that the adhesive composition (I-1) further contains a crosslinking agent.
The crosslinking agent crosslinks the adhesive resins (I-1 a) to each other, for example, by reacting with the functional groups.
Examples of the crosslinking agent include isocyanate crosslinking agents (i.e., crosslinking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy-based crosslinking agents (i.e., crosslinking agents having glycidyl groups) such as ethylene glycol glycidyl ether; triazine-based crosslinking agents (i.e., crosslinking agents having an aziridine group) such as Hexa [1- (2-methyl) -aziridinyl ] triphosphatriazine ] triazine triphosphate; metal chelate crosslinking agents (i.e., crosslinking agents having a metal chelate structure) such as aluminum chelates; isocyanurate-based crosslinking agents (i.e., crosslinking agents having an isocyanuric acid skeleton), and the like.
The crosslinking agent is preferably an isocyanate-based crosslinking agent from the viewpoint of improving the cohesive force of the adhesive agent and thereby improving the adhesive force of the adhesive layer, from the viewpoint of easy availability, and the like.
The crosslinking agent contained in the adhesive composition (I-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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, based on 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. Even when the adhesive composition (I-1) containing the photopolymerization initiator is irradiated with energy rays of relatively low energy such as ultraviolet rays, the curing reaction proceeds sufficiently.
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; acylphosphine oxide compounds such as phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide; sulfur 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, a quinone compound such as 1-chloroanthraquinone can be used; amine and the like.
The photopolymerization initiator contained in the adhesive composition (I-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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 not corresponding to any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additives include known additives such as antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments and dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts).
The reaction retarder is an additive for inhibiting the progress of an unintended crosslinking reaction in the adhesive composition (I-1) during storage, for example, by the action of a catalyst mixed in the adhesive composition (I-1). Examples of the reaction retarder include a reaction retarder that forms a chelate complex (chelate complex) with a chelate compound to a catalyst, and more specifically, a reaction retarder having two or more carbonyl groups (-C (=o) -) in 1 molecule.
The other additives contained in the adhesive composition (I-1) may be one or two or more, and when two or more are used, 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, and may be appropriately selected according to the kind thereof.
[ Solvent ]
The adhesive composition (I-1) may also contain a solvent. By containing the solvent, the adhesive composition (I-1) has improved coating suitability for the surface to be coated.
Preferably, the solvent is an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (e.g., carboxylic acid esters); 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 for producing the adhesive resin (I-1 a) from the adhesive resin (I-1 a), or may be added separately in the adhesive composition (I-1) with the same or a different solvent from the solvent used for producing the adhesive resin (I-1 a).
The solvent contained in the adhesive composition (I-1) may be one or two or more, and when two or more are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the solvent is not particularly limited, and may be appropriately adjusted.
< Adhesive composition (I-2) >
As described above, the adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2 a) having an unsaturated group introduced 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 an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group with a functional group in the adhesive resin (I-1 a).
The unsaturated group-containing compound is a compound having, in addition to the energy ray-polymerizable unsaturated group, 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).
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 adhesive resin (I-2 a) contained in the adhesive composition (I-2) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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 ]
For example, when the acrylic polymer having a structural unit derived from a functional group-containing monomer, which is the same as that in the adhesive resin (I-1 a), is used as the adhesive resin (I-2 a), it is preferable that the adhesive composition (I-2) further contains 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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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. Even if the adhesive composition (I-2) containing the photopolymerization initiator is irradiated with energy rays of relatively low energy such as ultraviolet rays, the curing reaction proceeds sufficiently.
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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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 not corresponding to any of the above-mentioned components within a range not impairing the effects of the present invention.
The other additives in the adhesive composition (I-2) may be the same as those in the adhesive composition (I-1).
The other additives contained in the adhesive composition (I-2) may be one or two or more, and when two or more are used, 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, and may be 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 one or two or more, and when two or more are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2), the content of the solvent is not particularly limited, and may be 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, relative to 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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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. Even if the adhesive composition (I-3) containing the photopolymerization initiator is irradiated with energy rays of relatively low energy such as ultraviolet rays, the curing reaction proceeds sufficiently.
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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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 not corresponding to any of the above-mentioned components within a range not impairing 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 one or two or more, and when two or more are used, 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, and may be 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) may be the same as the solvent in the adhesive composition (I-1).
The solvent contained in the adhesive composition (I-3) may be one or two or more, and when two or more are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-3), the content of the solvent is not particularly limited, and may be 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) have been described so far, and the materials described as the components contained therein can be used for all the adhesive compositions other than the three 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) include 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 a non-energy ray-curable adhesive composition containing an acrylic resin is preferable.
The adhesive compositions other than the adhesive compositions (I-1) to (I-3) preferably contain one or more kinds of crosslinking agents, and the content thereof may be set to the same content as in the case of the adhesive composition (I-1) and the like described above.
< Adhesive composition (I-4) >
As a preferable example of the adhesive composition (I-4), an adhesive composition containing the adhesive resin (I-1 a) and a crosslinking agent can be cited.
[ Adhesive resin (I-1 a) in adhesive composition (I-4) ]
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 adhesive resin (I-1 a) contained in the adhesive composition (I-4) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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, relative to the total mass of the adhesive composition (I-4).
[ Cross-linking agent ]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1 a), it is preferable that the adhesive composition (I-4) further contains a crosslinking agent.
The crosslinking agent in the adhesive composition (I-4) may be the same as the crosslinking agent in the adhesive composition (I-1).
The crosslinking agent contained in the adhesive composition (I-4) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the 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 not corresponding to any of the above-mentioned components within a range not impairing 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 one or two or more, and when two or more are used, 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, and may be 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) may be the same as the solvent in the adhesive composition (I-1).
The solvent contained in the adhesive composition (I-4) may be one or two or more, and when two or more are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-4), the content of the solvent is not particularly limited, and may be appropriately adjusted.
In the composite sheet for forming a protective film of the present invention, the adhesive layer is preferably non-energy ray-curable. This is because, if the adhesive layer is energy ray curable, simultaneous curing of the adhesive layer cannot be suppressed when the protective film forming film is cured by irradiation with energy rays. If the adhesive layer and the protective film forming film are cured at the same time, the cured protective film forming film and the adhesive layer are attached at the interface thereof to such an extent that peeling cannot be performed. 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 thus the protective film-attached semiconductor chip cannot be picked up normally. In the support sheet of the present invention, such a problem can be avoided with certainty by making the adhesive layer non-energy ray-curable, and the semiconductor chip with the protective film can be picked up more easily.
The effect of the adhesive layer being non-energy ray curable is described here, however, even if the layer of the support sheet in direct contact with the protective film forming film is a layer other than the adhesive layer, the same effect is exhibited as long as the layer is non-energy ray curable.
Adhesive composition preparation method of (2) >
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), can be obtained by blending the components constituting the adhesive composition, that is, by blending the adhesive and, if necessary, the components other than the adhesive.
The order of addition in blending the components is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be mixed with any blend component other than the solvent to pre-dilute the blend component, or the solvent may be mixed with any blend component other than the solvent to use the blend component without pre-diluting the blend component.
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, stirring blades, or the like; a method of mixing using a stirrer; 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 degraded, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃
Film for forming protective film
In the composite sheet for forming a protective film of the present invention, the adhesion between the protective film and the support sheet obtained by curing the film for forming a protective film is preferably 50 to 1500mN/25mm, more preferably 52 to 1450mN/25mm, and even more preferably 53 to 1430mN/25mm. When the adhesion force is equal to or higher than the lower limit value, the pickup of the semiconductor chip with the protective film outside the target can be suppressed, and the semiconductor chip with the protective film as the target can be picked up with high selectivity. Further, by setting the adhesion to the upper limit or less, breakage and chipping of the semiconductor chip can be suppressed when picking up the semiconductor chip with the protective film. In this way, by making the adhesion force within a specific range, the composite sheet for forming a protective film has good pickup suitability.
In this specification, even after the protective film forming film is cured, the laminated structure is referred to as a "protective film forming composite sheet" as long as the laminated structure of the cured product of the support sheet and 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 was 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 its protective film forming film.
Then, after the protective film forming film was cured by irradiation with energy rays to form a protective film, the support sheet was peeled from the protective film attached to the adherend at a peeling rate of 300 mm/min. The peeling at this time was 180 ° peeling, that is, the support sheet was peeled along the longitudinal direction thereof (the longitudinal direction of the composite sheet for forming the protective film) so that the surfaces of the protective film and the support sheet in contact with each other were at an angle of 180 ° to each other. Thereafter, 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 it is within a range in which the adhesive force can be stably detected, but is preferably 100 to 300mm. In addition, in the measurement, it is preferable that the composite sheet for forming a protective film is in a state of being attached to an adherend, and the attached state of the composite sheet for forming a protective film is stabilized.
In the present invention, the adhesion force between the protective film forming film and the support sheet is not particularly limited, and may be, for example, 80mN/25mm or more, but is preferably 100mN/25mm or more, more preferably 150mN/25mm or more, and particularly preferably 200mN/25mm or more. When the adhesion is set to 100mN/25mm or more, peeling of the protective film forming film from the support sheet can be suppressed at the time of dicing, and, for example, scattering of the semiconductor chip having the protective film forming film on the back surface from the support sheet can be suppressed.
On the other hand, the upper limit of the adhesion force between the protective film forming film and the support sheet is not particularly limited, and may be any of 4000mN/25mm, 3500mN/25mm, 3000mN/25mm, and the like, for example. These values are only one example.
That is, as one side surface, the adhesion force between the protective film forming film and the support sheet may be 80 to 4000mN/25mm, preferably 100 to 3500mN/25mm, more preferably 150 to 3500mN/25mm, and particularly preferably 200 to 3000mN/25mm.
The adhesion between the protective film forming film and the support sheet can be measured by the same method as that described above for the adhesion between the protective film and the support sheet except that the curing by irradiation of energy rays of the protective film forming film to be measured is not performed.
The adhesion between the protective film and the support sheet and the adhesion between the protective film forming film and the support sheet can be adjusted by, for example, adjusting the type 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 adhesion between the protective film or the film for forming a protective film and the supporting sheet can be more easily adjusted.
In addition, for example, when the layer of the support sheet on which the protective film forming film is provided is an adhesive layer, the constituent materials thereof can be appropriately adjusted by adjusting the types and amounts of the components contained in the adhesive layer. The kind and amount of the component contained in the adhesive layer can be adjusted by the kind and amount of the component contained in the adhesive composition.
On the other hand, when the layer of the support sheet on which the protective film forming film is provided is a base material, the adhesion 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 can be adjusted by, for example, performing the surface treatment as listed above as a treatment for improving the adhesion between the substrate and other layers, that is, by performing a concavity and convexity treatment by sandblasting, solvent treatment, or the like; oxidation treatments such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment; any of primer treatment and the like.
The protective film-forming film has an energy ray-curable property, and examples thereof include a protective film-forming film containing an energy ray-curable component (a).
The energy ray-curable component (a) is preferably uncured, preferably has tackiness, more preferably uncured and has tackiness.
The protective film-forming film may be formed of only one layer (single layer), or may be formed of a plurality of two or more layers, and when the protective film-forming film is formed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.
The thickness of the protective film-forming film is preferably 1 to 100. 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. Further, by setting the thickness of the protective film forming film to the above-described upper limit value or less, the thickness can be suppressed from becoming excessive.
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 may be 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 protective film-forming 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 applied to the surface to be formed of the protective film-forming film and dried as necessary, whereby the protective film-forming film can be formed at the target site. 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 components of the film for forming a protective film. Here, "normal temperature" is the same as described above.
The adhesive composition may be applied by a known method, and examples thereof include a method using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll knife coater, a curtain coater, a die coater, a blade coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying condition of the composition for forming a protective film is not particularly limited, but 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 ℃ for 10 seconds to 5 minutes.
< Composition (IV-1) for Forming protective film >
Examples of the composition for forming a protective film include a composition (IV-1) for forming a protective film containing the above-mentioned 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 crosslinked material at least a part of which is crosslinked with a crosslinking agent (f) described later, or may be an uncrosslinked material.
In the present specification, unless otherwise indicated, "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) obtained by polymerizing an acrylic polymer (a 11) having a functional group reactive with a group of another compound and an energy ray-curable compound (a 12) having an energy ray-curable group such as a group reactive with the functional group and an energy ray-curable double bond.
Examples of the functional group capable of reacting with a group of another compound in the acrylic polymer (a 11) include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group in which one or two hydrogen atoms of the amino group are replaced with groups other than hydrogen atoms), an epoxy group, and the like. Among them, the functional group is preferably a group other than a carboxyl group from the point of preventing corrosion of circuits such as a semiconductor wafer and a semiconductor chip.
Wherein preferably the functional group is a hydroxyl group.
Acrylic Polymer having functional group (a 11)
Examples of the acrylic polymer (a 11) having a functional group include a polymer obtained by copolymerizing an acrylic monomer having a functional group with an acrylic monomer having no functional group, and a polymer obtained by copolymerizing a monomer other than an acrylic monomer (a non-acrylic monomer) other than 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 such as vinyl alcohol and allyl alcohol (i.e., unsaturated alcohols having no (meth) acryl skeleton).
Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (i.e., monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (i.e., dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, citraconic acid, etc.; anhydrides of the ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
Preferably, the acrylic monomer having the functional group is a hydroxyl group-containing monomer, 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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The acrylic monomer having no functional group is preferably a (meth) acrylic acid alkyl ester having a chain structure in which the alkyl group constituting the alkyl ester has 1 to 18 carbon atoms, and examples thereof 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 (meth) acrylate, and palmityl (meth) acrylate, octadecyl (meth) acrylate (also referred to as stearic (meth) acrylate), and the like.
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, including aryl (meth) acrylates such as 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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
The non-acrylic monomer constituting the acrylic polymer (a 11) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer (a 11), the proportion (content) of the structural unit derived from the acrylic monomer having the functional group is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass, relative to the total mass of the structural units constituting the acrylic polymer (a 11). By setting the ratio to such a range, the degree of curing of the first protective film can be easily adjusted to a preferable range according to the content of the energy ray-curable group in the acrylic resin (a 1-1) obtained by copolymerization of the acrylic polymer (a 11) and the energy ray-curable compound (a 12).
The acrylic polymer (a 11) constituting the acrylic resin (a 1-1) may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Energy ray-curable Compound (a 12)
The energy ray-curable compound (a 12) preferably has one or more groups selected from the group consisting of isocyanate groups, epoxy groups, and carboxyl groups as groups that can react with functional groups of the acrylic polymer (a 11), and more preferably has isocyanate groups as the groups. For example, when the energy ray-curable compound (a 12) has an isocyanate group as the group, the isocyanate group easily reacts 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 in 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- (bisacryloxymethyl) 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 them, 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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The content of the acrylic resin (a 1-1) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass, relative to the total mass of the protective film-forming composition (IV-1) excluding the solvent.
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%. By making the ratio of the content in such a range, the adhesive force of the protective film formed by curing becomes larger. In addition, when the energy ray-curable compound (a 12) is a monofunctional (1 molecule having 1 of the groups), the upper limit of the content ratio is 100 mol%, and when the energy ray-curable compound (a 12) is a polyfunctional (1 molecule having 2 or more of the groups), the upper limit of the content ratio is sometimes more than 100 mol%.
The weight average molecular weight (Mw) of the polymer (a 1) is preferably 100000 ～ 2000000, more preferably 300000 ～ 1500000.
When the polymer (a 1) is a substance at least a part of which is crosslinked by the crosslinking agent (f), the polymer (a 1) may be a polymer obtained by copolymerizing a monomer having a group reactive with the crosslinking agent (f) and crosslinking the polymer (a 1) at a group reactive with the crosslinking agent (f) other than any of the above monomers described as monomers constituting the acrylic polymer (a 11), or a polymer obtained by crosslinking the polymer (a 12) at a group reactive with the functional group.
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 one kind or two or more kinds, and when two or more kinds are used, 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 of 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 groups include a (meth) acryloyl group, a vinyl group, and the like.
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.
The low molecular weight compound having an energy ray-curable group in the compound (a 2) includes, for example, a polyfunctional monomer or oligomer, and the like, and an acrylic compound having a (meth) acryloyl group is preferable.
Examples of the acrylic acid ester compounds 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, tricyclodecane dimethanol di (meth) acrylate (also referred to as tricyclodecane dimethyiol 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 (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, and the like;
Multifunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers, and the like.
As the epoxy resin having an energy ray-curable group or the phenol resin having an energy ray-curable group in the compound (a 2), for example, the resin described in paragraph 0043 or the like of "japanese patent application laid-open No. 2013-194102" can be used. Such a resin also corresponds to a resin constituting the thermosetting component (h) described later, but in the present invention, this is regarded as the compound (a 2).
The weight average molecular weight (Mw) of the compound (a 2) is preferably 100 to 30000, more preferably 300 to 10000.
The protective film-forming composition (IV-1) and the compound (a 2) contained in the protective film-forming film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
[ 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 substance crosslinked at least partially with the crosslinking agent (f), or may be a substance 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 them, the polymer (b) is preferably an acrylic polymer (hereinafter, abbreviated as "acrylic polymer (b-1)").
The acrylic polymer (b-1) may be a known acrylic polymer, and may be, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers and one or more monomers 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 group" is the same as that described hereinabove.
The alkyl (meth) acrylate is preferably a chain-structured alkyl (meth) acrylate having 1 to 18 carbon atoms, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (also referred to as lauryl (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (also referred to as myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, and palmityl (meth) acrylate, octadecyl (meth) acrylate (also referred to as stearic (meth) acrylate), and the like.
Examples of the (meth) acrylic acid ester having a cyclic skeleton include cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentyl (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.
Examples of the polymer (b) having no energy ray-curable group, at least a part of which is crosslinked by the crosslinking agent (f), include polymers obtained by reacting a reactive functional group in the polymer (b) 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, examples of the reactive functional group include 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. When 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, from the point of preventing corrosion of the circuit of the semiconductor wafer or the semiconductor chip, it is preferable that the reactive functional group is a group other than a carboxyl group.
Examples of the polymer (b) having the reactive functional group and not having an energy ray-curable group include a polymer obtained by polymerizing a monomer having at least the reactive functional group. In the case of the acrylic polymer (b-1), any one or both of the acrylic monomer and the non-acrylic monomer, which are exemplified as the monomers constituting the acrylic polymer (b-1), may be used. 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 other examples of the polymer (b) include a polymer obtained by polymerizing a monomer obtained by substituting the reactive functional group with one or more hydrogen atoms in the acrylic monomer or the non-acrylic monomer listed above.
In the polymer (b) having a reactive functional group, the proportion (content) of the structural unit derived from the monomer having a reactive functional group is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, relative to the total mass of the structural units constituting the polymer (b). 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 composition (IV-1) for forming a protective film and the polymer (b) having no energy ray-curable group contained in the film for forming a protective film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
The composition (IV-1) for forming a protective film includes a composition for forming a protective film containing either one or both of the polymer (a 1) and the compound (a 2). When the compound (a 2) is contained, the protective film-forming composition (IV-1) preferably further contains a polymer (b) having no energy ray-curable group, and in this case, the composition further preferably further contains the compound (a 1). The composition (IV-1) for forming a protective film may not contain the compound (a 2) and 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, based on 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 total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group relative to the total mass of the components other than the solvent (that is, the total content (mass) of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group relative to the total mass of the film for forming a protective film) is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, particularly preferably 15 to 70 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 composition (IV-1) for forming a protective film, the content of the energy ray-curable component (a) relative to the total content (total mass) of components other than the solvent (i.e., the content of the energy ray-curable component (a) relative to the total mass of the film for forming a protective film) is preferably 6 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 30% by mass, and particularly preferably 19.5 to 27% by mass. When the ratio of the total content is within such a range, the film formation becomes more excellent by curing suitably, and the deterioration of reliability due to excessive shrinkage during curing can be prevented.
When 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, per 100 parts by mass of the content 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, one or more 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 energy ray-curable component (a) and the 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; acylphosphine oxide compounds such as phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide; sulfur 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.
Further, 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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) is preferably 0.01 to 20 parts by mass, more preferably 2.0 to 12.0 parts by mass, and particularly preferably 2 to 10 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable compound (a) in the composition (IV-1) for forming a protective film.
[ Filler (d) ]
By including the filler (d) in the protective film-forming film, adjustment of the thermal expansion coefficient of the protective film obtained by curing the protective film-forming film is facilitated, and by optimizing the thermal expansion coefficient with respect to the object to be formed of the protective film, the reliability of the package obtained by using the composite sheet for forming the protective film is further improved. Further, by containing the filler (d) in the protective film forming film, the moisture absorption rate of the protective film can be reduced or the heat radiation property can be improved.
Examples of the filler (d) include a filler 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.
Preferable examples of the inorganic filler include powders such as silica, alumina, talc, calcium carbonate, titanium white, red lead, silicon carbide, and boron nitride; 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.
Among them, the inorganic filler is preferably silica or alumina, more preferably epoxy-modified silica.
The average particle diameter of the filler (d) is not particularly limited, but is preferably 0.01 to 20. Mu.m, more preferably 0.08 to 15. Mu.m, still more preferably 0.1 to 10. Mu.m, still more preferably 0.3 to 10. Mu.m, particularly preferably 0.5 to 8. 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 addition, unless otherwise specified, the "average particle diameter" in the present specification refers to a value of the particle diameter (D 50) at which the cumulative value is 50% in the particle size distribution curve obtained by the laser diffraction scattering method.
The composition (IV-1) for forming a protective film and the filler (d) contained in the film for forming a protective film may be one kind only or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the filler (d) is used, the content of the filler (d) 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 (total mass) of all components except the solvent (i.e., the content of the filler (d) based on the total mass of the protective film-forming film). By setting the content of the filler (d) to such a range, the adjustment of the thermal expansion coefficient described above becomes easier.
As one side of the present invention, the content of the filler (d) is preferably 5 to 83 mass%, more preferably 5 to 70 mass%, relative to the total mass of the protective film-forming film.
As another side of the present invention, when the average particle diameter of the filler (d) is 0.08 to 0.15 μm, the content of the filler (d) is preferably 5 to 83% by mass, more preferably 5 to 70% by mass, relative to the total mass of the film for forming a protective film.
As still another aspect of the present invention, when the average particle diameter of the filler (d) is 0.5 to 8 μm, the content of the filler (d) is preferably 5 to 8% by mass relative to the total mass of the film for forming a protective film.
By setting the content of the filler (d) to such a range, it is easier to adjust the surface roughness (Ra) of the surface (β) of at least one side of the film for forming a protective film to 0.04 μm or more, more preferably 0.049 μm or more, and it is easier to adjust the surface roughness (Ra) of the surface (β) to 0.15 μm or less, more preferably 0.129 μm or less.
That is, when the content of the filler (d) is adjusted to the above range, it is easier to adjust the surface roughness (Ra) of the surface (β) of at least one side of the protective film-forming film to preferably 0.04 to 0.15 μm, and more preferably 0.049 to 0.129 μm.
[ Coupling agent (e) ]
By using a substance having a functional group reactive 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. In addition, 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 reactive 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 dimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazole silane.
The protective film-forming composition (IV-1) and the coupling agent (e) contained in the protective film-forming film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the coupling agent (e) is used, the content of the coupling agent (e) 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, based on 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 in the protective film-forming composition (IV-1) and the protective film-forming film. By setting the content of the coupling agent (e) to the lower limit value or more, the effect of using the coupling agent (e) such as an improvement in dispersibility of the filler (d) in the resin, an improvement in adhesiveness between the protective film-forming film and the adherend, and the like can be obtained more remarkably. Further, by setting the content of the coupling agent (e) to the upper limit value or less, the occurrence of degassing can be further suppressed.
[ Cross-linking agent (f) ]
The initial adhesion and cohesion of the film for forming a protective film can be adjusted by crosslinking the energy ray-curable component (a) or the polymer (b) having no energy ray-curable group using 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 abbreviated 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 or the like with a polyol compound. The "adduct" refers to a reaction product of the aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound with a low-molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, and examples thereof include a xylylene diisocyanate adduct of trimethylolpropane as described below. The term "terminal isocyanate urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at a terminal part of a 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 in which any one or two or more of toluene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are added 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-aziridinyl carboxamide) triethylenemelamine.
When the organic polyisocyanate compound is used as the crosslinking agent (f), a hydroxyl group-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, the energy ray-curable component (a), or the polymer (b) having no energy ray-curable group has a hydroxyl group, the crosslinked 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 composition (IV-1) for forming a protective film and the crosslinking agent (f) contained in the film for forming a protective film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the crosslinking agent (f) is used, the content of the crosslinking agent (f) 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, based on 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 in the protective film-forming composition (IV-1). By making the content of the crosslinking agent (f) be the lower limit value or more, the effect produced by using the crosslinking agent (f) can be obtained more remarkably. Further, by setting the content of the crosslinking agent (f) to the upper limit value or less, 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 the organic dye include amines(Aminium) a dye, a cyanine dye, a merocyanine dye, a croconium dye, a squaraine dye, and chamomile blue(Azulenium) pigmenting, polymethine pigmenting, naphthoquinone pigmenting, pyranA pigment, phthalocyanine pigment, naphthalocyanine pigment, naphthalenide (naphtholactam) 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 salt dye), dithiol metal complex pigment, indophenol pigment, triallylmethane pigment, anthraquinone pigment, naphthol pigment, azone pigment, benzimidazolone pigment, pyranthrone pigment, and petrolatum (threne) 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 (i.e., indium tin oxide) based pigment, ATO (i.e., antimony tin oxide) based pigment, and the like.
The composition (IV-1) for forming a protective film and the colorant (g) contained in the film for forming a protective film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the colorant (g) is used, the content of the colorant (g) in the protective film-forming film may be appropriately adjusted according to the purpose. For example, the protective film may be printed 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) relative to the total content of all the components except the solvent (i.e., the content of the colorant (g) relative to the total mass of 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. By making the content of the colorant (g) be the lower limit value or more, the effect produced by using the colorant (g) can be obtained more remarkably. Further, by setting the content of the colorant (g) to the 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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the 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 one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Epoxy resin (h 1)
The epoxy resin (h 1) includes known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and its hydrogenated products, o-cresol novolac epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, and epoxy compounds having a double function or more such as phenylene skeleton type epoxy resins.
As the epoxy resin (h 1), an epoxy resin having an unsaturated hydrocarbon group can be used. The epoxy resin having an unsaturated hydrocarbon group has a higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the composite sheet for forming a protective film is improved.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a part of the epoxy groups of a multifunctional epoxy resin is converted into groups having an unsaturated hydrocarbon group. Such a compound can be 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, a (meth) acrylamide group, and the like, and acryl groups are preferable.
The number average molecular weight of the epoxy resin (h 1) is not particularly limited, and is preferably 300 to 30000, more preferably 400 to 10000, particularly preferably 500 to 3000, from the viewpoint 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 indicated, "number average molecular weight" refers to a number average molecular weight expressed in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).
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, which can be measured according to the method of JIS K7236:2001.
The epoxy resin (h 1) may be used alone or in combination of two or more, and when two or more are used at the same time, the combination and ratio thereof may be arbitrarily selected.
Thermosetting 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 two or more functional groups capable of reacting with an epoxy group in 1 molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group, and the functional group is preferably a phenolic hydroxyl group, an amino group, or an acid group, and more preferably a phenolic hydroxyl group or an amino group.
Examples of the phenolic curing agent having a phenolic hydroxyl group in the thermosetting agent (h 2) include polyfunctional phenol resins, biphenol, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-phenol resins.
Examples of amine curing agents having an amino group in the heat curing agent (h 2) include dicyandiamide (hereinafter, abbreviated as "dic") and the like.
The thermosetting agent (h 2) may 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 the 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 the phenol resin, and the like.
The unsaturated hydrocarbon group in the thermosetting agent (h 2) is the same as that in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.
When a phenol curing agent is used as the thermosetting agent (h 2), the thermosetting agent (h 2) is preferably a thermosetting agent having a high softening point or glass transition temperature, since the thermosetting agent (h 2) is initiated from a point of improving the peelability of the protective film from the support sheet.
The number average molecular weight of the resin component of the thermosetting agent (h 2), for example, the polyfunctional phenol resin, the novolak phenol resin, the dicyclopentadiene phenol resin, the aralkyl phenol resin and the like is preferably 300 to 30000, more preferably 400 to 10000, and particularly preferably 500 to 3000.
The molecular weight of the non-resin component such as biphenol or dicyandiamide in the thermosetting agent (h 2) 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 two or more kinds, and when two or more kinds are used at the same time, the combination and ratio thereof may be arbitrarily selected.
When the thermosetting component (h) is used, the content of the thermosetting agent (h 2) is preferably 0.01 to 20 parts by mass per 100 parts by mass of the content of the epoxy resin (h 1) in the composition (IV-1) for forming a protective film and the film for forming a protective film.
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)) 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 in the composition (IV-1) for forming a protective film and the film for forming a protective film.
[ General additive (z) ]
The general-purpose additive (z) may be a known additive, and may be arbitrarily selected according to the purpose, and is not particularly limited, and examples of preferable additives include plasticizers, antistatic agents, antioxidants, and capturing agents (GETTERING AGENT).
The composition (IV-1) for forming a protective film and the general-purpose additive (z) contained in the film for forming a protective film may be one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
When the general-purpose additive (z) is used, 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 (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 one or two or more, and when two or more are used, 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, from the viewpoint of enabling more uniform mixing of the components contained in the composition (IV-1) for forming a protective film.
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 can be obtained by blending the components for constituting the composition.
The order of addition in blending the components is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be mixed with any blend component other than the solvent to pre-dilute the blend component, or the solvent may be mixed with any blend component other than the solvent to use the blend component without pre-diluting the blend component.
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, stirring blades, or the like; a method of mixing using a stirrer; 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 degraded, and the temperature is preferably 15 to 30 ℃.
As a composite sheet which is attached to the back surface opposite to the circuit surface of the semiconductor wafer or the semiconductor chip and has a layer exhibiting adhesiveness on the support sheet, the same composite sheet for forming a protective film of the present invention, there is a dicing die bonding sheet (DICING DIE bonding sheet).
However, the adhesive layer provided in the dicing die bonding sheet functions as an adhesive for attaching the semiconductor chip to a substrate, a lead frame, or another semiconductor chip or the like after being picked up together with the semiconductor chip from the supporting sheet. On the other hand, the protective film forming film in the composite sheet for forming a protective film of the present invention is the same as the adhesive layer in that it is picked up together with the semiconductor chip from the supporting sheet, but it finally becomes a protective film by curing, and has the 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 from the use of the adhesive layer in the dicing die bonding sheet, and the intended performance is certainly different. In addition, the protective film forming film generally tends to be hard and difficult to pick up as compared with the adhesive layer in the dicing die bonding sheet, which also reflects the difference in the above-described applications. Therefore, it is generally very difficult to directly transfer the adhesive layer in the dicing die bonding sheet to the film for forming a protective film in the composite sheet for forming a protective film. The composite sheet for forming a protective film of the present invention has excellent pick-up suitability for a semiconductor chip with a protective film, which has not been conventionally known, as a composite sheet having a film for forming a protective film having energy ray curability.
Method for producing composite sheet for forming protective film
The composite sheet for forming a protective film of the present invention can be manufactured by sequentially laminating the above layers in a corresponding positional relationship. The method of forming each layer is the same as described hereinabove.
For example, in the case of producing a support sheet, when an adhesive layer is laminated on a substrate, the adhesive composition may be applied to the substrate and dried as necessary.
On the other hand, for example, when 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 and the protective film forming film may be directly formed. The same method can be used for the layers other than the protective film forming film, and the layers can be laminated on the adhesive layer using the composition for forming the layers. In this way, when a laminated structure of two continuous layers is formed using an arbitrary composition, a composition may be further coated on a layer formed of the composition to form a new layer.
Among these, the composition is preferably used to form a layer stacked later of the two layers on another release film, and the formed layer is bonded to the exposed surface of the other layer formed on the side opposite to the side in contact with the release film, thereby forming a continuous two-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, when a composite sheet for forming a protective film (a support sheet is a composite sheet for forming a protective film of a laminate of a base material and an adhesive layer) obtained by laminating an adhesive layer on a base material and laminating a film for forming a protective film on the adhesive layer is produced, the adhesive layer is laminated on the base material by applying the adhesive composition to the base material and drying it as needed, and the protective film-forming composition is further applied to a release film and drying it as needed, thereby forming a film for forming a protective film on the release film. Then, the exposed surface of the protective film forming film is bonded to the exposed surface of the adhesive layer laminated on the substrate, and the protective film forming film is laminated on the adhesive layer, whereby a composite sheet for forming a protective film can be obtained.
In addition, when an adhesive layer is laminated on a substrate, instead of the method of applying the adhesive composition to the substrate as described above, the adhesive composition may be applied to a release film and dried as necessary, whereby an adhesive layer is formed on the release film, and the exposed surface of the layer is bonded to the surface of one side of the substrate, whereby the adhesive layer can be laminated on the substrate.
In any method, the release film may be removed at any timing after the target laminated structure is formed.
As described above, the layers constituting the composite sheet for forming a protective film other than the base material may be formed on the release film in advance and laminated on the surface of the target layer, and thus the composite sheet for forming a protective film may be produced by appropriately selecting the layers in such a process as needed.
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 (e.g., protective film forming film) on the opposite side of the support sheet. Therefore, even when the composition for forming the outermost layer, such as the composition for forming a protective film, is applied onto a release film (preferably, a release treated surface thereof) and dried as necessary, the outermost layer is formed on the release film, and other layers are laminated on an exposed surface of the layer on the opposite side to the side in contact with the release film by any of the above methods, and the release film is bonded without being removed, the composite sheet for forming a protective film can be obtained.
Method for using composite sheet for forming protective film
The composite sheet for forming a protective film of the present invention can be used by the following method, for example.
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 through the protective film forming film. Then, the protective film-forming film is irradiated with energy rays, and the protective film-forming film is cured to form a protective film. Then, the semiconductor wafer is divided together with the protective film by dicing, and semiconductor chips are manufactured. Then, the semiconductor chip is separated from the support sheet and picked up in a state where the protective film is attached (i.e., as a semiconductor chip with a protective film).
Then, the semiconductor chip of the obtained semiconductor chip with the protective film is flip-chip bonded to the circuit surface of the substrate by the same method as the conventional method, and then a semiconductor package is fabricated. Then, using the semiconductor package, a target semiconductor device may be fabricated.
In addition, although the case where the protective film is formed by curing the protective film-forming film and then cutting is described here, the order of performing these steps may be reversed when the composite sheet for protective film formation of the present invention is used. That is, after the protective film forming composite sheet is attached to the back surface of the semiconductor wafer, the semiconductor wafer is divided by dicing together with the protective film forming film, and the semiconductor chips are manufactured. Then, the divided protective film forming film is irradiated with energy rays, and the protective film forming film is cured to form a protective film. Then, the semiconductor chip with the protective film is separated from the support plate in the same manner as described above to be picked up, and the target semiconductor device may be fabricated.
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 (Nippon Kayaku Co., ltd., "KAYARAD R-684", bifunctional ultraviolet-curable compound, molecular weight 304)
Polymers without energy-ray-curable groups
(B) -1: acrylic resin (weight average molecular weight 300000, glass transition temperature-1 ℃ C.) (obtained by copolymerizing butyl acrylate (hereinafter abbreviated as "BA") (10 parts by mass), methyl acrylate (hereinafter abbreviated as "MA") (70 parts by mass), glycidyl methacrylate (hereinafter abbreviated as "GMA") (5 parts by mass), and 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") (15 parts by mass))
Photopolymerization initiator
(C) -1:2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (manufactured by BASF corporation "Irgacure (registered trademark) 369")
(C) -2:1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime) (manufactured by BASF corporation "Irgacure (registered trademark) OXE 02")
Filler material
(D) -1: silica filler (fused silica filler, average particle size 8 μm)
Coupling agent
(E) -1: 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Co., ltd., "KBM-503", silane coupling agent)
Coloring agent
(G) -1: 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 177,177) were mixed, and the three pigments were colored so that the total amount of the three pigments/styrene acrylic resin amount=1/3 (mass ratio) was obtained
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) -1, the photopolymerization initiator (c) -2, 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, parts by mass) thereof became the values shown in table 1, and stirred at 23 ℃.
(Preparation of adhesive composition (I-4))
A non-energy ray-curable adhesive composition (I-4) containing an acrylic polymer (100 parts by mass, solid content) and a trifunctional xylylene diisocyanate-based crosslinking agent (10.7 parts by mass, solid content, "TAKENATE D N" manufactured by MITSUI chemical POLYURETHANES, INC.) and further containing methyl ethyl ketone as a solvent at a solid content concentration of 30% by mass was prepared. The acrylic polymer was a 2-ethylhexyl acrylate (hereinafter abbreviated as "2 EHA") (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass) copolymerized to have a weight average molecular weight of 600,000.
(Production of supporting sheet)
The adhesive composition (I-4) obtained above was applied to the release treated surface of a release film (SP-PET 381031, manufactured by Lintec corporation, thickness 38 μm) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and was dried by heating at 120℃for 2 minutes, thereby forming a non-energy ray-curable adhesive layer having a thickness of 10 μm.
Next, a polypropylene film (young's modulus 400MPa, thickness 80 μm) as a base material was bonded to the exposed surface of the adhesive layer, thereby obtaining a support sheet (10) -1 having the adhesive layer on one surface of the base material.
(Production of composite sheet for Forming protective film)
The protective film-forming composition (IV-1) obtained above was applied onto the release-treated surface of a release film (SP-PET 381031 manufactured by Lintec corporation, thickness 38 μm) obtained by releasing one side of a polyethylene terephthalate film by silicone treatment, and dried at 100 ℃ for 2 minutes, thereby producing an energy ray-curable protective film-forming film (13) -1 having a thickness of 25 μm.
Then, the release film was removed from the adhesive layer of the support sheet (10) -1 obtained as described above, and the exposed surface of the protective film forming film (13) -1 obtained as described above was bonded to the exposed surface of the adhesive layer, whereby a composite sheet for forming a protective film was produced in which the base material, the adhesive layer, the protective film forming film (13) -1, and the release film were laminated in this order in the thickness direction thereof. The composition of the obtained composite sheet for forming a protective film is shown in table 2.
< Evaluation of composite sheet for Forming protective film >
The obtained composite sheet for forming a protective film was irradiated with ultraviolet light from the support sheet side to the test piece before curing under the conditions of illuminance 195mW/cm 2 and light quantity 170mJ/cm 2 using an ultraviolet irradiation device ("RAD 2000m/8" manufactured by Lintec corporation), whereby the film (13) -1 for forming a protective film was cured to obtain a test piece after curing.
Next, the base material and the adhesive layer were removed from the cured test piece, and the test piece was subjected to JIS Z0237:2010, the ball tack value at an inclination angle of 30 ° was measured for the exposed surface of the protective film obtained by curing the protective film forming film (13) -1. The measurement results are shown in Table 2.
(Evaluation of cover tape adhesion)
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 a film (13) -1 for forming a protective film, and the sheet was further fixed to an annular frame and allowed to stand for 30 minutes.
Next, the protective film-forming film (13) -1 was cured by irradiating the protective film-forming composite sheet with ultraviolet light from the support sheet (10) -1 side under conditions of an illuminance of 195mW/cm 2 and a light amount of 170mJ/cm 2 using an ultraviolet irradiation apparatus ("RAD 2000m/8" manufactured by Lintec corporation), to thereby produce a protective film.
Then, the silicon wafer was sliced 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 thickness of 3mm×3mm in a lateral direction.
Next, 20 silicon chips with protective films were picked up using a chip bonder (die bonder) (manufactured by Canon Machinery inc. BESTEM-D02).
On an iron plate of 12cm in the longitudinal direction and 12cm in the transverse direction and having a thickness of 5mm, 16 silicon chips with protective films obtained as described above were placed at grid-like positions of 4 squares in the longitudinal direction and 4 squares in the transverse direction so that the intervals therebetween were uniform, and a cover tape (Sumitomo Bakelite co., ltd. CSL-Z7302 manufactured by ltd.) of 12cm in the longitudinal direction and 3.8cm 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, so that the pressure applied to the silicon chips with protective films was set to 350gf, and heated for one minute. Then, the metal plate was removed, the cover tape was peeled off, and whether the silicon chip with the protective film was attached to the cover tape was tested. The results are shown in Table 2.
As a determination method, a case where even one of the 16 silicon chips with protective films is attached to the cover tape was determined as "B", and a case where none of the 16 silicon chips with protective films is attached to the cover tape was determined as "a".
Example 2
< Production and evaluation of composite sheet for Forming protective film >
A protective film-forming composition (IV-1) was prepared in the same manner as in example 1, except that the content (blending amount) of 20 parts by mass of the energy ray-curable component (a 2) -1 was replaced with 30 parts by mass as shown in table 1.
Energy ray-curable protective film-forming films (13) to 25 were produced in the same manner as in example 1 except that the protective film-forming composition (IV-1) obtained above was used.
Then, a composite sheet for forming a protective film was produced in the same manner as in example 1, except that the protective film forming film (13) -1 was replaced with the protective film forming film (13) -25. The composition of the obtained composite sheet for forming a protective film is shown in table 2.
Using the composite sheet for forming a protective film obtained above, the measurement of the ball tack value and the evaluation of the cover tape adhesion were performed in the same manner as in example 1. The results are shown in Table 2.
Example 3
< Production and evaluation of composite sheet for Forming protective film >
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 0.3 parts by mass of the photopolymerization initiator (c) -1 was replaced with 1.0 parts by mass and the content (blending amount) of 0.3 parts by mass of the photopolymerization initiator (c) -2 was replaced with 1.0 parts by mass as shown in table 1.
Energy ray-curable protective film-forming films (13) to 26 having a thickness of 25 μm were produced in the same manner as in example 1, except that the protective film-forming composition (IV-1) obtained above was used.
Then, a composite sheet for forming a protective film was produced in the same manner as in example 1, except that the protective film forming film (13) -1 was replaced with the protective film forming film (13) -26. The composition of the obtained composite sheet for forming a protective film is shown in table 2.
Using the composite sheet for forming a protective film obtained above, the measurement of the ball tack value and the evaluation of the cover tape adhesion were performed in the same manner as in example 1. The results are shown in Table 2.
Comparative example 1
< Production and evaluation of composite sheet for Forming protective film >
A protective film-forming composition (IV-1) was prepared in the same manner as in example 1, except that the content (blending amount) of 20 parts by mass of the energy ray-curable component (a 2) -1 was replaced with 5 parts by mass as shown in table 1.
Energy ray-curable protective film-forming films (13) to 27 having a thickness of 25 μm were produced in the same manner as in example 1, except that the protective film-forming composition (IV-1) obtained above was used.
Then, a composite sheet for forming a protective film was produced in the same manner as in example 1, except that the protective film forming film (13) -1 was replaced with the protective film forming film (13) -27. The composition of the obtained composite sheet for forming a protective film is shown in table 2.
Using the composite sheet for forming a protective film obtained above, the measurement of the ball tack value and the evaluation of the cover tape adhesion were performed in the same manner as in example 1. The results are shown in Table 2.
Comparative example 2
< Production and evaluation of composite sheet for Forming protective film >
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 0.3 part by mass of the photopolymerization initiator (c) -1 was replaced with 0.1 part by mass and the content (blending amount) of 0.3 part by mass of the photopolymerization initiator (c) -2 was replaced with 0.1 part by mass as shown in table 1.
Energy ray-curable protective film-forming films (13) to 28 having a thickness of 25 μm were produced in the same manner as in example 1, except that the protective film-forming composition (IV-1) obtained above was used.
Then, a composite sheet for forming a protective film was produced in the same manner as in example 1, except that the protective film forming film (13) -1 was replaced with the protective film forming films (13) -28. The composition of the obtained composite sheet for forming a protective film is shown in table 2.
Using the composite sheet for forming a protective film obtained above, the measurement of the ball tack value and the evaluation of the cover tape adhesion were performed in the same manner as in example 1. The results are shown in Table 2.
TABLE 1
TABLE 2
As is apparent from the above results, in the case of using the composite sheet for forming a protective film of examples 1 to 3, the protective film was formed in accordance with JIS Z0237:2010 is set to a ball tackiness value of 2 or less measured at an inclination angle of 30 DEG, and the semiconductor chip with the protective film is inhibited from adhering to the cover tape.
In contrast, when the composite sheet for forming a protective film of comparative examples 1 to 2 was used, the protective film was formed in accordance with JIS Z0237:2010, the ball tack value measured at an inclination angle of 30 degrees was 3 to 4, presumably being easily attached to the cover tape.
In the case of using the composite sheet for forming a protective film of comparative example 1, the proportion of the content of the energy ray-curable component (a) relative to the total content of the components other than the solvent in the composition (IV-1) for forming a protective film is as small as 5.8 mass%, and therefore it is presumed that the energy ray curing is insufficient, and the ball tackiness value becomes large. On the other hand, in the case of using the composite sheet for forming a protective film of comparative example 2, the content of the photopolymerization initiator (c) in the film for forming a protective film was as low as 1 part by mass per 100 parts by mass of the energy ray-curable component (a), and therefore, it was presumed that the curing of the composite sheet for forming a protective film was insufficient, resulting in an increase in the rolling ball tackiness value.
Industrial applicability
The present invention is useful for manufacturing semiconductor devices and is therefore industrially useful.
Description of the reference numerals
1A, 1B, 1C, 1D, 1E: a protective film-forming composite sheet; 2F: a protective film-forming sheet; 10: support sheet, 10a: the surface of the support sheet; 11: a substrate; 11a: a surface of the substrate; 12: an adhesive layer; 12a: the surface of the adhesive layer; 13. 23: a protective film forming film; 13a, 23a: a surface of the protective film forming film; 15: stripping the film; 15': a first release film; 15": a second release film; 16: an adhesive layer for jigs; 16a: the surface of the adhesive layer for the clamp; 101: a semiconductor chip with a protective film; 102: embossing the carrier tape; 102a: embossing the carrier tape pocket; 103: and (5) a cover tape.

Claims (10)

1. An application of an energy ray-curable film in the manufacture of a film for forming a back protective film of a semiconductor wafer or a semiconductor chip,
The back surface of the semiconductor wafer or the semiconductor chip is the surface of the semiconductor wafer or the semiconductor chip opposite to the electrode forming surface,
Wherein the protective film forming film has the protective film according to JIS Z0237 when the protective film is formed by irradiation of energy rays: 2010 are determined at an inclination angle of 30 DEG, and the ball tack value is 2 or less.
2. The use according to claim 1, wherein the film for forming a back surface protective film of a semiconductor wafer or a semiconductor chip comprises an energy ray-curable component (a).
3. The use according to claim 2, wherein the film for forming a back surface protective film of a semiconductor wafer or a semiconductor chip further comprises a photopolymerization initiator (c).
4. The use according to claim 3, wherein the content of the photopolymerization initiator (c) is 2.0 to 12.0 parts by mass per 100 parts by mass of the energy ray-curable component (a).
5. The use according to claim 1, wherein the film for forming a back surface protective film of a semiconductor wafer or a semiconductor chip further contains 5 to 83 mass% of a filler (d) with respect to the total mass of the film for forming a back surface protective film of a semiconductor wafer or a semiconductor chip,
The filling material (d) is an inorganic filling material, and the inorganic filling material is powder of silicon dioxide, aluminum oxide, talcum, calcium carbonate, titanium white, red lead, silicon carbide or boron nitride; beads obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; or glass fibers.
6. An energy ray-curable film and a use of a support sheet for producing a composite sheet for forming a back protective film of a semiconductor wafer or a semiconductor chip, wherein,
The back surface of the semiconductor wafer or the semiconductor chip is the surface of the semiconductor wafer or the semiconductor chip opposite to the electrode forming surface,
The energy ray-curable film is provided on the support sheet,
The energy ray-curable film, when irradiated with energy rays to form a protective film, has the protective film and is in accordance with JIS Z0237:2010 are determined at an inclination angle of 30 DEG, and the ball tack value is 2 or less.
7. A method for manufacturing a semiconductor device with a protective film using a film for forming a protective film, the method comprising:
(1) Attaching a protective film forming film to the back surface of the semiconductor wafer;
(2) A step of irradiating the protective film-forming film with energy rays to form a protective film from the protective film-forming film; and
(3) A step of dicing the semiconductor wafer to produce semiconductor chips,
The protective film forming film is an energy ray-curable protective film forming film, the back surface of the semiconductor wafer is the surface of the semiconductor wafer opposite to the electrode forming surface,
The film for forming a protective film comprises an energy ray-curable component (a), a polymer (b) having no energy ray-curable group, and a photopolymerization initiator (c),
The content of the energy ray-curable component (a) is 6 to 50% by mass relative to the total mass of the film for forming the protective film,
The content of the photopolymerization initiator (c) is 2.0 to 12.0 parts by mass per 100 parts by mass of the energy ray-curable component (a),
The film for forming a protective film has the protective film and is formed according to JIS Z0237 when the protective film is formed by irradiation of energy rays: 2010 are determined at an inclination angle of 30 DEG, and the ball tack value is 2 or less.
8. The method for manufacturing a semiconductor device according to claim 7, wherein,
The protective film-forming film further contains 5 to 83 mass% of a filler (d) relative to the total mass of the protective film-forming film,
The filling material (d) is an inorganic filling material, and the inorganic filling material is powder of silicon dioxide, aluminum oxide, talcum, calcium carbonate, titanium white, red lead, silicon carbide or boron nitride; beads obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; or glass fibers.
9. A method for manufacturing a semiconductor device with a protective film using a composite sheet for forming a protective film, the method comprising the steps of:
(1) Attaching a protective film forming film to the back surface of the semiconductor wafer;
(2) A step of irradiating the protective film-forming film with energy rays to form a protective film from the protective film-forming film; and
(3) A step of dicing the semiconductor wafer to produce semiconductor chips,
The composite sheet for forming a protective film comprises a film for forming a protective film on a support sheet,
The protective film forming film is an energy ray-curable protective film forming film, the back surface of the semiconductor wafer is the surface of the semiconductor wafer opposite to the electrode forming surface,
The film for forming a protective film comprises an energy ray-curable component (a), a polymer (b) having no energy ray-curable group, and a photopolymerization initiator (c),
The content of the energy ray-curable component (a) is 6 to 50% by mass relative to the total mass of the film for forming the protective film,
The content of the photopolymerization initiator (c) is 2.0 to 12.0 parts by mass per 100 parts by mass of the energy ray-curable component (a),
The film for forming a protective film has the protective film and is formed according to JIS Z0237 when the protective film is formed by irradiation of energy rays: 2010 are determined at an inclination angle of 30 DEG, and the ball tack value is 2 or less.
10. The method for manufacturing a semiconductor device according to claim 9, wherein,
The protective film-forming film further contains 5 to 83 mass% of a filler (d) relative to the total mass of the protective film-forming film,
The filling material (d) is an inorganic filling material, and the inorganic filling material is powder of silicon dioxide, aluminum oxide, talcum, calcium carbonate, titanium white, red lead, silicon carbide or boron nitride; beads obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; or glass fibers.
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