CN115124743A - Protective film forming film, composite sheet for forming protective film, and method for producing chip with protective film - Google Patents
Protective film forming film, composite sheet for forming protective film, and method for producing chip with protective film Download PDFInfo
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- CN115124743A CN115124743A CN202210072759.5A CN202210072759A CN115124743A CN 115124743 A CN115124743 A CN 115124743A CN 202210072759 A CN202210072759 A CN 202210072759A CN 115124743 A CN115124743 A CN 115124743A
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- protective film
- film
- forming
- meth
- energy ray
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- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
Abstract
The present invention provides an energy ray-curable protective film forming film, which contains an acrylic resin (b) having no energy ray-curable group and an inorganic filler (d), wherein the acrylic resin (b) has a weight average molecular weight of 1100000 or less and a dispersity of greater than 3.0, and wherein the ratio of the total content of components other than the inorganic filler (d) to the content of the inorganic filler (d) in the protective film forming film is 40% by mass or more.
Description
Technical Field
The present invention relates to a protective film forming film, a composite sheet for forming a protective film, and a method for manufacturing a chip with a protective film.
The present application claims priority based on Japanese patent application No. 2021-055012, filed in Japan on 3/29/2021, and the contents thereof are incorporated herein.
Background
Wafers such as semiconductor wafers and insulator wafers include a wafer having a circuit formed on one surface (circuit surface) thereof and further having bump electrodes such as bumps (bumps) on the surface (circuit surface). Such a wafer can be divided into chips and mounted on a circuit board by connecting its projecting electrodes to connection pads (connection pads) on the circuit board.
In such a wafer or chip, in order to suppress damage such as cracking, a surface (back surface) opposite to a circuit surface may be protected by a protective film.
In order to form such a protective film, a protective film forming film for forming a protective film is attached to the back surface of the wafer. The protective film forming film may be used in a state of being laminated on a support sheet for supporting the protective film forming composite sheet, or may be used without being laminated on the support sheet. Next, the wafer having the protective film forming film on the back surface is processed into chips having the protective film on the back surface (chips with the protective film) through various subsequent steps. Such chips with protective films are mounted on a circuit board after being picked up, thereby constituting various substrate devices (e.g., semiconductor devices).
In the protective film forming film, there is a non-curable protective film forming film which does not have curability and functions as a protective film in its original state. When a film is formed using a non-curable protective film, a chip with a protective film can be manufactured at low cost by a simplified method since a curing step is not required. On the other hand, when a curable protective film is used to form a film, the cured product thereof is used as a protective film, and therefore, there is an advantage that the wafer protective performance is high. In addition, a thermosetting protective film forming film cured by heating has a long heating time at the time of curing, but an energy ray-curable protective film forming film cured by irradiation with an energy ray has an advantage that irradiation with an energy ray at the time of curing can be completed in a short time. Therefore, various energy ray-curable protective film-forming films have been developed (see patent document 1).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2019/082959
Disclosure of Invention
Technical problems to be solved by the invention
However, regardless of the presence or absence of curability of the protective film forming film, the protective film may be peeled from the wafer or chip as an adherend after being attached to the back surface of the wafer and after the final formation of various substrate devices. For example, when the wafer is divided into chips, when the protective film is cut to a chip size, when the chip with the protective film is picked up, and in the substrate device, the protective film may be peeled off from the wafer or the chip. When the protective film forming film is curable, there is also a possibility that the protective film is peeled off from the wafer or the chip at the time of curing thereof.
Therefore, if the peeling can be suppressed in the energy ray-curable protective film formation film, the utility will be higher.
The purpose of the present invention is to provide a protective film forming film that is an energy ray-curable protective film forming film and that can suppress the peeling of a protective film from a wafer or a chip after the protective film is formed from the protective film attached to the wafer, a protective film forming composite sheet provided with the protective film forming film, and a method for manufacturing a chip with a protective film using the protective film forming film or the protective film forming composite sheet.
Means for solving the problems
The present invention provides an energy ray-curable protective film forming film, wherein the protective film forming film contains an acrylic resin (b) having no energy ray-curable group and an inorganic filler (d), the acrylic resin (b) has a weight average molecular weight of 1100000 or less and a dispersity of greater than 3.0, and the ratio of the total content of components other than the inorganic filler (d) to the content of the inorganic filler (d) in the protective film forming film is 40% by mass or more.
The protective film-forming film of the present invention may further contain a polyfunctional urethane (meth) acrylate oligomer as the energy ray-curable component (a).
The present invention provides a composite sheet for forming a protective film, which comprises a support sheet and a protective film forming film provided on one surface of the support sheet, wherein the protective film forming film is the protective film forming film of the present invention.
The invention provides a method for manufacturing a chip with a protective film, which is provided with a chip and a protective film arranged on the back surface of the chip, wherein the method for manufacturing the chip with the protective film comprises the following steps: a step of preparing a first laminated film in which the protective film forming film of the present invention and a wafer are laminated in the thickness direction thereof by attaching the protective film forming film to the back surface of the wafer, or preparing a first laminated composite sheet in which the support sheet, the protective film forming film and the wafer are laminated in the thickness direction thereof in this order by attaching the protective film forming film of the composite sheet for forming a protective film of the present invention to the back surface of the wafer; a step of forming the protective film by energy ray curing the protective film forming film in the first laminated film or the first laminated composite sheet, thereby producing a second laminated film formed by laminating the protective film and the wafer in the thickness direction thereof, or producing a second laminated composite sheet formed by laminating the support sheet, the protective film, and the wafer in this order in the thickness direction thereof; a step of producing a third laminated film in which a plurality of chips with a protective film are fixed to the dicing sheet by dividing the wafer in the second laminated film and cutting the protective film in a state in which the dicing sheet is provided on the protective film side of the second laminated film, or producing a third laminated composite sheet in which a plurality of chips with a protective film are fixed to the supporting sheet by dividing the wafer in the second laminated composite sheet and cutting the protective film; and picking up the chip with the protective film by pulling the chip with the protective film in the third laminated film away from the dicing sheet, or pulling the chip with the protective film in the third laminated composite sheet away from the supporting sheet.
Effects of the invention
According to the present invention, there can be provided a protective film forming film which is an energy ray-curable protective film forming film capable of suppressing peeling of a protective film from a wafer or a chip after the protective film is formed from the protective film attached to the wafer, a protective film forming composite sheet provided with the protective film forming film, and a method for manufacturing a chip with a protective film using the protective film forming film or the protective film forming composite sheet.
Drawings
Fig. 1 is a sectional view schematically showing one example of a protective film forming film of one embodiment of the present invention.
Fig. 2 is a sectional view schematically showing an example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 3 is a sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 4 is a sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 5 is a sectional view schematically showing another example of the composite sheet for forming a protective film according to the embodiment of the present invention.
Fig. 6A is a sectional view for schematically illustrating one example of a method for manufacturing a chip with a protective film according to one embodiment of the present invention.
Fig. 6B is a sectional view for schematically illustrating an example of a method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 6C is a sectional view for schematically illustrating an example of a method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 6D is a sectional view for schematically illustrating one example of a method for manufacturing a chip with a protective film according to one embodiment of the present invention.
Fig. 6E is a sectional view for schematically illustrating an example of a method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 7A is a sectional view for schematically illustrating another example of the method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 7B is a sectional view for schematically illustrating another example of the method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 7C is a sectional view for schematically illustrating another example of the method of manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 7D is a sectional view for schematically illustrating another example of the method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 7E is a sectional view for schematically illustrating another example of the method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 8A is a sectional view for schematically illustrating another example of the method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 8B is a sectional view for schematically illustrating another example of the method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 8C is a sectional view for schematically illustrating another example of the method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Fig. 8D is a sectional view for schematically illustrating another example of the method for manufacturing a chip with a protective film according to an embodiment of the present invention.
Description of the reference numerals
10. 20: a support sheet; 10a, 20 a: one face (first face) of the support sheet; 11: a substrate; 12: an adhesive layer; 13. 23: a protective film forming film (energy ray-curable protective film forming film); 13': a protective film; 13 b': the other surface (second surface) of the protective film; 130': a cut-off protective film; 101. 102, 103, 104: a composite sheet for forming a protective film; 501: a first laminated composite sheet; 502: a second laminated composite sheet; 503: a third laminate composite sheet; 601: a first laminated film; 602: a second laminated film; 603: a third laminated film; 8: cutting the slices; 9: a wafer; 9 b: the back side of the wafer; 90: a chip; 90 b: the back side of the chip; 901: and a chip with a protective film.
Detailed Description
O protective film forming film
The protective film forming film according to one embodiment of the present invention is energy ray-curable, and contains an acrylic resin (b) having no energy ray-curable group (which may be simply referred to as "acrylic resin (b)" in the present specification) and an inorganic filler (d), the acrylic resin (b) having a weight average molecular weight of 1100000 or less and a dispersity of more than 3.0, and the proportion of the total content of components other than the inorganic filler (d) to the content of the inorganic filler (d) in the protective film forming film is 40 mass% or more.
The protective film forming film of the present embodiment is a film for providing a protective film on a chip to protect the chip.
By using the protective film-forming film of the present embodiment or the composite sheet for protective film formation provided with the protective film-forming film of the present embodiment, a chip with a protective film provided on the back surface of the chip and a chip provided with a protective film can be manufactured.
The chip with the protective film can be manufactured, for example, by: after a protective film forming film is attached to the back surface of the wafer, the protective film is formed by curing the protective film forming film, the wafer is divided into chips, and the protective film is cut along the outer peripheries of the chips.
In this specification, examples of the "wafer" include a semiconductor wafer made of an elemental semiconductor such as silicon, germanium, or selenium, or a compound semiconductor such as GaAs, GaP, InP, CdTe, ZnSe, or SiC; an insulator wafer made of an insulator such as sapphire or glass.
In this specification, a surface of the wafer on which the circuit is formed is referred to as a "circuit surface". The surface of the wafer opposite to the circuit surface is referred to as a "back surface".
The wafer is divided into chips by dicing or the like. In the present specification, as in the case of a wafer, a surface of a chip on which a circuit is formed is referred to as a "circuit surface", and a surface of the chip opposite to the circuit surface is referred to as a "back surface".
Bump electrodes such as bumps and posts (pilars) are provided on both the circuit surface of the wafer and the circuit surface of the chip. The bump electrode is preferably made of solder.
Further, by using the chip with the protective film, a substrate device can be manufactured.
In the present specification, the term "substrate device" refers to a device in which a chip with a protective film is flip-chip connected to connection pads on a circuit board at projecting electrodes on the circuit surface. For example, when a semiconductor wafer is used as the wafer, a semiconductor device is used as the substrate device.
By making the protective film forming film of the present embodiment contain the acrylic resin (b) and the inorganic filler (d) having a weight average molecular weight and a dispersity within specific ranges and making the ratio of the total content of the components other than the inorganic filler (d) in the protective film forming film to the content of the inorganic filler (d) to be a specific value or more, it is possible to suppress peeling of the protective film from the wafer or the chip after the protective film is formed therefrom by curing of the protective film forming film attached to the wafer.
The protective film forming film of the present embodiment is energy ray-curable, and may or may not be thermosetting. When the protective film forming film of the present embodiment has both of the energy ray curability and the thermosetting property, the energy ray curing of the protective film forming film contributes to the formation of the protective film more than the heat curing.
In the present specification, "energy ray" refers to a ray having an energy quantum in an electromagnetic wave or a charged particle beam. Examples of the energy ray include ultraviolet rays, radiation, and electron beams. For example, the ultraviolet rays may be irradiated by using a high-pressure mercury lamp, a fusion lamp (fusion lamp), a xenon lamp, a black light lamp, an LED lamp, or the like as the ultraviolet ray source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray-curable property" refers to a property of curing by irradiation with an energy ray, and "non-energy ray-curable property" refers to a property of not curing even by irradiation with an energy ray.
The term "non-curable" refers to a property that curing does not proceed by any means such as heating or irradiation with energy rays.
The curing conditions for forming the protective film by curing the protective film forming film with an energy ray are not particularly limited as long as the protective film is formed with a curing degree to such an extent that the function thereof is sufficiently exhibited, and may be appropriately selected depending on the kind of the protective film forming film.
For example, the illuminance of the energy ray when the energy ray-curable protective film is cured by an energy ray is preferably 60 to 320mW/cm 2 . The amount of the energy ray during curing is preferably 100 to 1000mJ/cm 2 。
The protective film-forming film preferably contains the acrylic resin (b), the inorganic filler (d), and components other than these (acrylic resin (b) and inorganic filler (d)).
Examples of the protective film-forming film include a protective film-forming film containing the energy ray-curable component (a), the acrylic resin (b) (acrylic resin (b) having no energy ray-curable group), and the inorganic filler (d).
The components contained in the protective film forming film will be described in detail later.
The protective film forming film preferably satisfies the condition of storage modulus E' shown below.
That is, the storage modulus E ' of a test piece for a protective film forming film having a thickness of 200 μm (hereinafter, simply referred to as "protective film forming test piece") as a laminate of a plurality of protective film forming films was measured between two points of a test piece for a protective film forming film (hereinafter, simply referred to as "protective film forming test piece") held at intervals of 20mm at a temperature range of-10 ℃ to 140 ℃ under measurement conditions of a tensile mode at a frequency of 11Hz and a temperature rise rate of 3 ℃/min, and the storage modulus E ' of the test piece for a protective film forming film at this time was 70 ℃. '. 70 Preferably 30MPa or less, more preferably 10MPa or less, and still more preferably 5MPa or less. By making the storage modulus E' 70 When the upper limit value is less than the above-described upper limit value, the protective film forming film can be more easily attached to the object to be attached (wafer).
The storage modulus E' 70 The lower limit of (b) is not particularly limited. E.g. storage modulus E' 70 The protective film forming film of 0.5MPa or more can be manufactured more easily and form a protective film of more excellent characteristics.
In the present specification, the term "thickness" refers to an average value of thicknesses measured at 5 randomly selected points on an object, and can be obtained using a constant pressure thickness gauge in accordance with JIS K7130, unless otherwise specified, without being limited to the test piece.
The length of the protective film-forming film test piece in the stretching direction in the stretching mode is not particularly limited as long as the measurement accuracy of the storage modulus E' is not impaired, but is preferably 30mm or more.
In the measurement of the storage modulus E' of the test piece of the protective film-forming film, it is preferable to increase the temperature of the test piece at a constant rate.
In the measurement of the storage modulus E' of the test piece of the protective film-forming film, the Amplitude is preferably 5 μm.
The protective film of the energy ray cured product of the protective film forming film preferably satisfies the following condition of storage modulus E'.
That is, the illuminance was 200mW/cm 2 The light quantity was 300mJ/cm 2 Under the conditions (1), a laminate of a plurality of protective film forming films having a thickness of 50 μm was irradiated with ultraviolet rays having a wavelength of 365nm twice from each of both sides thereof to cure the protective film forming films, thereby obtaining a protective film test piece (herein, it may be simply referred to as "protective film test piece"), two positions of the protective film test piece were held with a space of 20mm, and the storage modulus E ' of the protective film test piece was measured between the two positions in a temperature range of 0 to 300 ℃ under measurement conditions of a tensile mode having a frequency of 11Hz and a temperature rise rate of 3 ℃/min, and the storage modulus E ' of the protective film test piece at 130 ℃ at this time ' 130 Preferably 5MPa or more, more preferably 8MPa or more, and still more preferably 10MPa or more. By making the storage modulus E' 130 If the lower limit value is higher than the above-described lower limit value, the protective effect of the protective film on the object to be attached (wafer) is further enhanced.
The storage modulus E' 130 The upper limit of (3) is not particularly limited. For example, storage modulus E' 130 A protective film having 3000MPa or less can be produced easily, and has more excellent characteristics.
The length of the protective film test piece in the tensile direction in the tensile mode is not particularly limited as long as the measurement accuracy of the storage modulus E' is not impaired, but is preferably 30mm or more.
In the measurement of the storage modulus E' of the protective film test piece, the temperature of the test piece is preferably raised at a constant rate.
When the storage modulus E' of the protective film test piece is measured, the Amplitude is preferably 5 μm.
The storage modulus E 'of the protective film-forming test piece and the protective film test piece (in other words, the storage modulus E' of the protective film-forming film and the protective film) can be adjusted by adjusting the kind and content of components contained in the protective film-forming composition described later, particularly the acrylic resin (b) having no energy ray-curable group, the energy ray-curable component (a), the inorganic filler (d), and the like.
For example, the storage modulus E' of the test piece of the protective film forming film can be reduced by increasing the content of a low molecular weight component, which is a polymer component such as the energy ray-curable component (a) described later, in the protective film forming film. In addition, by increasing the content of the inorganic filler (d) described later in the protective film forming film, the storage modulus E' of the protective film forming film test piece can also be reduced.
On the other hand, by increasing the content of the energy ray-curable component (a) described later in the protective film forming film, the storage modulus E' of the protective film test piece can be increased. In addition, the storage modulus E' of the protective film test piece can also be increased by reducing the content of the inorganic filler (d) described later in the protective film forming film.
The protective film forming film may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers. When the protective film forming film is composed of a plurality of layers, these plurality of layers may be the same as each other or different from each other, and the combination of these plurality of layers is not particularly limited.
In the present specification, not only the protective film forming film, "a plurality of layers may be the same or different from each other" means "all layers may be the same or different from each other, or only some layers may be the same", and further "a plurality of layers are different from each other" means "at least one of the constituent material and the thickness of each layer is different from each other".
The thickness of the protective film forming film is preferably 1 to 100 μm, more preferably 3 to 80 μm, and particularly preferably 5 to 60 μm. When the thickness of the protective film forming film is not less than the lower limit value, a protective film having higher protective performance can be formed. By making the thickness of the protective film forming film equal to or less than the upper limit value, the thickness of the chip with the protective film can be prevented from becoming excessively thick.
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.
< composition for Forming protective film >
The protective film forming film can be formed using an energy ray-curable composition for forming a protective film (in this specification, it may be simply referred to as "a composition for forming a protective film") containing a constituent material of the protective film forming film. For example, the protective film-forming film can be formed by applying the protective film-forming composition to the surface to be formed and drying it as necessary. The content ratio between 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 between the components in the protective film forming film. In the present specification, "normal temperature" refers to a temperature at which cooling or heating is not particularly performed, that is, a normal temperature, and includes, for example, a temperature of 18 to 28 ℃.
In the protective film forming film, the ratio of the total content of one or two or more of the components contained in the protective film forming film, which will be described later, to the total mass of the protective film forming film is not more than 100 mass%.
Similarly, in the composition for forming a protective film, the ratio of the total content of one or two or more of the components to be described later in the composition for forming a protective film to the total mass of the composition for forming a protective film is not more than 100% by mass.
The coating of the composition for forming a protective film may be carried out by a known method, and examples thereof include methods using various coating machines such as a knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater (knife coater), a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the protective film-forming composition are not particularly limited. However, when the composition for forming a protective film contains a solvent described later, it is preferably dried by heating. The protective film-forming composition containing a solvent is preferably dried by heating at 70 to 130 ℃ for 10 seconds to 5 minutes, for example. However, it is preferable that the composition for forming a protective film having thermosetting properties is dried by heating so that the composition itself and the thermosetting protective film-forming film formed from the composition are not thermally cured.
< composition (IV) for Forming an energy ray-curable protective film >
Examples of a preferable composition for forming a protective film include an energy ray-curable composition (IV) for forming a protective film (hereinafter, simply referred to as "composition (IV)") containing the acrylic resin (b) having no energy ray-curable group, the energy ray-curable component (a), and the inorganic filler (d).
[ acrylic resin (b) having no energy ray-curable group ]
The acrylic resin (b) is a component for imparting film formability to the protective film and suppressing peeling of the protective film from the above-mentioned wafer or chip.
The acrylic resin (b) may be a known acrylic resin, and may be, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers and one or more monomers (non-acrylic monomers) other than the acrylic monomers.
At least a part of the acrylic resin (b) may be crosslinked by a crosslinking agent or may not be crosslinked.
Examples of the acrylic monomer constituting the acrylic resin (b) include (meth) acrylates such as alkyl (meth) acrylates having no functional group and a cyclic skeleton, (meth) acrylates having a glycidyl group, (meth) acrylates having a hydroxyl group, (meth) acrylates having a substituted amino group, (meth) acrylates having a carboxyl group, and (meth) acrylates having an amino group; (meth) acrylamide; and (meth) acrylamide derivatives such as 4- (meth) acryloylmorpholine. The "substituted amino group" refers to a group having a structure in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom. The "functional group" refers to a group (reactive functional group) capable of reacting with another group, such as a glycidyl group, a hydroxyl group, a substituted amino group, a carboxyl group, or an amino group.
In the present specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". Terms similar to those of (meth) acrylic acid are also the same, and for example, "(meth) acrylate" is a concept including both "acrylate" and "methacrylate", and "(meth) acryl" is a concept including both "acryl" and "methacryl".
In the present specification, assuming a structure in which one or more hydrogen atoms in a specific compound are substituted with a group other than a hydrogen atom, a compound having the above-described substituted structure is referred to as a "derivative" of the above-described specific compound.
In this specification, the "group" includes not only an atomic group in which a plurality of atoms are bonded but also one atom.
Examples of the alkyl (meth) acrylate having no functional group and no cyclic skeleton include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), and the like, Alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is 1 to 18 carbon atoms, such as tridecyl (meth) acrylate, tetradecyl (meth) acrylate ((myristyl (meth) acrylate)), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate ((palm (meth) acrylate)), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate ((stearyl (meth) acrylate)).
Examples of the (meth) acrylate having no functional group and a cyclic skeleton include cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate;
aralkyl (meth) acrylates such as benzyl (meth) acrylate;
cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate;
cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate, and the like.
Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate and the like.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxyl group-containing (meth) acrylates having a structure in which one or two or more hydrogen atoms are substituted with a hydroxyl group in either one of the alkyl (meth) acrylate having no functional group and a cyclic skeleton and the (meth) acrylate having no functional group and a cyclic skeleton. Examples of the preferable 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 resin (b) include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
Examples of the acrylic resin (b) at least a part of which is crosslinked by the crosslinking agent include acrylic resins obtained by reacting functional groups in the acrylic resin (b) with the crosslinking agent.
The functional group may be appropriately selected depending on the kind of the crosslinking agent, and the like, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, the functional group includes a hydroxyl group, a carboxyl group, an amino group, and the like, and among them, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the crosslinking agent is an epoxy compound, examples of the functional group include a carboxyl group and an amino group, and among them, a carboxyl group having high reactivity with an epoxy group is preferable. However, from the viewpoint of preventing the circuit of the wafer or chip from corroding, the functional group is preferably a group other than a carboxyl group.
Examples of the acrylic resin (b) having the functional group include acrylic resins obtained by polymerizing a monomer having at least the functional group.
More specifically, the acrylic resin (b) having the functional group includes, for example, an acrylic resin obtained by polymerizing one or more monomers selected from the group consisting of the glycidyl group-containing (meth) acrylate, the hydroxyl group-containing (meth) acrylate, the substituted amino group-containing (meth) acrylate, the carboxyl group-containing (meth) acrylate, the amino group-containing (meth) acrylate, and a monomer having a structure in which one or two or more hydrogen atoms in the non-acrylic monomer are substituted with the functional group.
In the acrylic resin (b) having a functional group, the proportion (content) of the amount of the structural unit derived from the monomer having a functional group to the total amount of the structural units constituting the acrylic resin (b) is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. By making the ratio within the above range, the degree of crosslinking in the acrylic resin (b) is within a more preferable range.
The weight average molecular weight (Mw) of the acrylic resin (b) is 1100000 or less, preferably 1000000 or less, and may be, for example, 800000 or less and 600000 or less. By setting the weight average molecular weight of the acrylic resin (b) to the upper limit or less, the effect of suppressing the peeling of the protective film from the wafer or chip becomes higher.
The lower limit of the weight average molecular weight of the acrylic resin (b) is not particularly limited. For example, the weight average molecular weight of the acrylic resin (b) is preferably 10000 or more from the viewpoint that the film forming property of the composition (IV) is further improved.
The weight average molecular weight of the acrylic resin (b) can be appropriately adjusted within a range set by arbitrarily combining any of the lower limit values and any of the upper limit values. For example, in one embodiment, the weight average molecular weight of the acrylic resin (b) is preferably 10000 to 1100000, more preferably 10000 to 1000000, and may be, for example, any one range of 10000 to 800000 and 10000 to 600000. However, these ranges are only an example of the weight average molecular weight of the acrylic resin (b).
In the present specification, unless otherwise specified, "weight average molecular weight" refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.
The dispersibility (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the acrylic resin (b) is greater than 3.0 (greater than 3.0), preferably 3.1 or more, and may be, for example, any one of 3.4 or more and 3.7 or more. By setting the degree of dispersion of the acrylic resin (b) to the lower limit or more, the effect of suppressing the peeling of the protective film from the wafer or chip becomes higher.
The upper limit of the degree of dispersion of the acrylic resin (b) is not particularly limited. For example, the degree of dispersion of the acrylic resin (b) is preferably 6 or less from the viewpoint of suppressing the transfer of the low-molecular-weight acrylic resin (b).
The degree of dispersion of the acrylic resin (b) can be appropriately adjusted within a range set by arbitrarily combining any of the lower limit values and the upper limit value described above. For example, in one embodiment, the dispersion degree of the acrylic resin (b) is preferably more than 3.0 and 6 or less, more preferably 3.1 to 6, and may be, for example, any one of 3.4 to 6 and 3.7 to 6. However, these ranges are only one example of the degree of dispersion of the acrylic resin (b).
As the acrylic resin (b), for example, acrylic resins having a weight average molecular weight (Mw) in any one range of 1100000 or less, 1000000 or less, 800000 or less, and 600000 or less, and a dispersity of 3.0 or more, 3.1 or more, 3.4 or more, and 3.7 or more can be cited.
The acrylic resin (b) contained in the composition (IV) and the protective film-forming film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (IV), the proportion of the content of the acrylic resin (b) relative to the total content of all the components except the solvent (i.e., the proportion of the content of the acrylic resin (b) in the protective film forming film relative to the total mass of the protective film forming film) is preferably 8 mass% or more, more preferably 10 mass% or more, and may be, for example, any one of 12 mass% or more and 14 mass% or more. When the ratio is not less than the lower limit value, the effect of suppressing the peeling of the protective film from the wafer or the chip becomes higher.
In the composition (IV), the upper limit value of the proportion of the content of the acrylic resin (b) to the total content of all the components except the solvent (i.e., the proportion of the content of the acrylic resin (b) in the protective film forming film to the total mass of the protective film forming film) is not particularly limited. The ratio is preferably 25 mass% or less from the viewpoint of well-balanced performance of the property of suppressing peeling of the protective film from the wafer or the chip and the properties other than the property.
In the composition (IV), the ratio of the content of the acrylic resin (b) to the total content of all the components except the solvent (i.e., the ratio of the content of the acrylic resin (b) in the protective film-forming film to the total mass of the protective film-forming film) may be appropriately adjusted within a range set by arbitrarily combining any of the lower limit value and the upper limit value described above. For example, in one embodiment, the ratio is preferably 8 to 25% by mass, more preferably 10 to 25% by mass, and may be in any range of 12 to 25% by mass and 14 to 25% by mass. However, these ranges are only one example of the ratios.
[ inorganic Filler (d) ]
By adjusting the amounts of the composition (IV) and the inorganic filler (d) in the protective film-forming film, the thermal expansion coefficient of a cured product (for example, a protective film) of the protective film-forming film can be more easily adjusted while preventing the peeling of the protective film from the wafer or chip. For example, by optimizing the thermal expansion coefficient of the protective film with respect to the object to be formed with the protective film, the reliability of the package formed by forming the film using the protective film is further improved. Further, by using the protective film forming film containing the inorganic filler (d), the moisture absorption rate of a cured product (for example, a protective film) of the protective film forming film can be reduced, and the heat release property can be improved.
Examples of the inorganic filler (d) include powders of inorganic materials such as silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, 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 fibers, and the like.
Among them, the inorganic filler (d) is preferably silica or alumina.
The amount of the inorganic filler (d) contained in the composition (IV) and 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.
In the composition (IV), the proportion of the content of the inorganic filler (d) to the total content of all the components except the solvent (i.e., the proportion of the content of the inorganic filler (d) in the protective film-forming film to the total mass of the protective film-forming film) is preferably 35 to 75 mass%, and may be, for example, any one of 45 to 70 mass% and 50 to 65 mass%. By making the ratio within the above range, the characteristics of the protective film forming film are not impaired, and the effect by using the inorganic filler (d) becomes higher.
[ energy ray-curable component (a) ]
The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray, and is also a component for imparting film-forming properties, flexibility, and the like to the protective film and forming a hard protective film after curing. By further containing the energy ray-curable component (a), the protective film forms a protective film having good properties.
In the protective film forming film, the energy ray-curable component (a) is preferably uncured, preferably adhesive, and more preferably uncured and adhesive.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80000 to 2000000, and a compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000. At least a part of the polymer (a1) may be crosslinked by a crosslinking agent, or may not be crosslinked.
(a polymer (a1) having an energy ray-curable group and a weight-average molecular weight of 80000 to 2000000.)
Examples of the polymer (a1) having energy-ray-curable groups and a weight-average molecular weight of 80000 to 2000000 include an acrylic resin (a1-1) obtained by reacting an acrylic polymer (a11) having a functional group capable of reacting with a group of another compound with an energy-ray-curable compound (a12) 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 include a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group having a structure in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom), an epoxy group, and the like. Among them, the functional group is preferably a group other than a carboxyl group in order to prevent corrosion of circuits of wafers, chips, and the like.
Among them, the functional group is preferably a hydroxyl group.
Acrylic Polymer having functional group (a11)
Examples of the acrylic polymer having a functional group (a11) include a polymer obtained by copolymerizing an acrylic monomer having the functional group and an acrylic monomer having no functional group, and a polymer obtained by further copolymerizing a monomer other than an acrylic monomer (non-acrylic monomer) in addition to these monomers.
The acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known polymerization method may be used.
Examples of the acrylic monomer having the functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and non (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols having no (meth) acryloyl skeleton).
Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of said ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate.
The acrylic monomer having the functional group is preferably a hydroxyl group-containing monomer.
The acrylic monomer having the functional group constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the acrylic monomer having no such functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, isopropyl (meth) acrylate, dodecyl (meth) acrylate, and (meth) acrylate, dodecyl (meth) acrylate, and (meth) acrylate, Alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is a carbon number of 1 to 18, such as tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate).
Examples of the acrylic monomer having no functional group include (meth) acrylates containing an alkoxyalkyl group such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate; aromatic group-containing (meth) acrylates such as aryl (meth) acrylates including phenyl (meth) acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; and non-crosslinkable (meth) acrylic esters having a tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.
The acrylic monomer having no functional group constituting the acrylic polymer (a11) may be one type alone, or two or more types may be used, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.
The non-acrylic monomer constituting the acrylic polymer (a11) may be one kind only, or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer (a11), the proportion (content) of the amount of the structural unit derived from the acrylic monomer having the functional group to the total amount of the structural units constituting the polymer is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 3 to 30% by mass. By making the ratio within the above range, the content of the energy ray-curable group in the acrylic resin (a1-1) obtained by copolymerization of the acrylic polymer (a11) and the energy ray-curable compound (a12) can be adjusted to a preferable range of the degree of curing of the protective film.
The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
The content of the acrylic resin (a1-1) in the protective film forming film is preferably 1 to 70 mass%, more preferably 5 to 60 mass%, and particularly preferably 10 to 50 mass% with respect to the total mass of the protective film forming film.
Energy ray-curable compound (a12)
The energy ray-curable compound (a12) preferably has one or more groups selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a group capable of reacting with the functional group of the acrylic polymer (a11), and more preferably has an isocyanate group as the group. When the energy ray-curable compound (a12) has an isocyanate group as the group, for example, the isocyanate group is easily reacted with a hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
The number of the energy ray-curable groups of one molecule of the energy ray-curable compound (a12) is not particularly limited, and may be appropriately selected in consideration of physical properties such as shrinkage rate required for the target protective film.
For example, the energy ray-curable compound (a12) preferably has 1 to 5 energy ray-curable groups in one molecule, and more preferably has 1 to 3 energy ray-curable groups.
Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloxymethyl) ethyl isocyanate;
an acryloyl monoisocyanate compound obtained by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
and an acryloyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth) acrylate.
Among them, 2-methacryloyloxyethyl isocyanate is preferable as the energy ray-curable compound (a 12).
The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be one kind only, or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. When the content ratio is within the above range, the adhesive force of the cured product of the protective film-forming film is further increased. In addition, when the energy ray-curable compound (a12) is a monofunctional compound (having one group in one molecule), the upper limit of the proportion of the content is 100 mol%, but when the energy ray-curable compound (a12) is a polyfunctional compound (having two or more groups in one molecule), the upper limit of the proportion of the content may be more than 100 mol%.
The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000 to 2000000, more preferably 300000 to 1500000.
Wherein "weight average molecular weight" is as described above.
The polymer (a1) contained in the composition (IV) and the protective film-forming film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
(Compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000.)
Examples of the energy ray-curable group in the compound (a2) having an energy ray-curable group and a molecular weight of 100 to 80000 include groups containing an energy ray-curable double bond, and preferable examples thereof include a (meth) acryloyl group, a vinyl group and the like.
As long as the above conditions are satisfied, the compound (a2) is not particularly limited, and examples thereof include a low molecular weight compound having an energy ray-curable group, an epoxy resin having an energy ray-curable group, a phenol resin having an energy ray-curable group, and the like.
Examples of the low molecular weight compound having an energy ray-curable group in the compound (a2) include polyfunctional monomers and oligomers, and acrylate compounds having a (meth) acryloyl group are preferable.
Examples of the acrylate compound include polyfunctional monomers and oligomers, and polyfunctional acrylate compounds having two or more (meth) acryloyl groups in one molecule are preferred.
Examples of the polyfunctional acrylate compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxypolyethoxy) phenyl ] propane, ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxydiethoxy) phenyl ] propane, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, 2-bis [4- ((meth) acryloyloxypropyloxy) phenyl ] propane, tricyclodecanedimethanol di (meth) acrylate (also known as tricyclodecanedimethylol di (meth) acrylate), 1, 10-decanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, difunctional (meth) acrylates having two (meth) acryloyl groups in one molecule) such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, and the like;
polyfunctional (meth) acrylates having three or more (meth) acryloyl groups in one molecule) such as tris (2- (meth) acryloyloxyethyl) isocyanurate, epsilon-caprolactone-modified tris- (2- (meth) acryloyloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, and dipentaerythritol hexa (meth) acrylate;
and a polyfunctional (meth) acrylate oligomer (a (meth) acrylate oligomer having two or more (meth) acryloyl groups in one molecule) such as a polyfunctional urethane (meth) acrylate oligomer.
As the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group in the compound (a2), for example, compounds described in japanese patent application laid-open No. 2013-194102, paragraph 0043, and the like can be used. The resin described above is also a resin constituting a thermosetting component described later, but it is regarded as the compound (a2) in the composition (IV).
The weight average molecular weight of the compound (a2) is preferably 100 to 30000, more preferably 300 to 10000.
The compound (a2) contained in the composition (IV) and the protective film-forming film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
The protective film-forming film preferably contains the compound (a2), more preferably contains a polyfunctional acrylate compound having two or three or more (meth) acryloyl groups in one molecule, and further preferably contains a polyfunctional urethane (meth) acrylate oligomer as the energy ray-curable component (a). The protective film forming film containing the energy ray-curable component (a) is a cured product (protective film) formed by irradiation with an energy ray, and has excellent protective properties, flexibility, and particularly excellent characteristics.
When the composition (IV) and the protective film forming film contain the energy ray-curable component (a), the content of the energy ray-curable component (a) in the composition (IV) and the protective film forming film is preferably 100 to 310 parts by mass, more preferably 130 to 280 parts by mass, for example, 130 to 200 parts by mass, and further 210 to 280 parts by mass, relative to 100 parts by mass of the content of the acrylic resin (b).
In the composition (IV), the ratio of the total content of the energy ray-curable component (a) and the acrylic resin (b) to the total content of all the components except the solvent (i.e., the ratio of the total content of the energy ray-curable component (a) and the acrylic resin (b) in the protective film forming film to the total mass of the protective film forming film) is preferably 10 to 60% by mass, and may be, for example, any one of 20 to 50% by mass and 30 to 45% by mass. When the ratio is within the above range, the effect of using the energy ray-curable component (a) and the acrylic resin (b) is further enhanced.
[ other ingredients ]
The composition (IV) and the protective film-forming film may further contain other components not belonging to any of the acrylic resin (b), the inorganic filler (d) and the energy ray-curable component (a) within a range not impairing the effects of the present invention.
Examples of the other components include a photopolymerization initiator (c), a coupling agent (e), a crosslinking agent (f), a colorant (g), a thermosetting component (h), a general-purpose additive (z), and a polymer (b0) having no energy ray-curable group (which is not an acrylic resin (b) (in the present specification, may be referred to as "other polymer (b 0)" or "polymer (b 0)" having no energy ray-curable group), and the like.
((photopolymerization initiator (c))
When the composition (IV) and the protective film-forming film contain the photopolymerization initiator (c), the polymerization (curing) reaction of the energy ray-curable component (a) can be efficiently performed.
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-phenylpropan-1-one, 2-dimethoxy-1, 2-diphenylethan-1-one, 2-hydroxy-1- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one, and 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; alpha-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as diacetyl; benzil (benzil); dibenzoyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
Examples of the photopolymerization initiator include photosensitizers such as amines.
The composition (IV) and the photopolymerization initiator (c) contained in the protective film-forming film may be one type or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
When the photopolymerization initiator (c) is used, the content of the photopolymerization initiator (c) in the composition (IV) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, relative to 100 parts by mass of the energy ray-curable component (a).
(coupling agent (e))
When the composition (IV) and the protective film-forming film contain the coupling agent (e) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness and close adhesion of the protective film-forming film to an adherend are increased. Further, the heat resistance of a cured product (for example, a protective film) having a protective film-forming film is not impaired, and the water resistance is improved.
The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the acrylic resin (b), the energy ray-curable component (a), and the like, and more preferably a silane coupling agent.
Examples of the preferable silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and the like, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.
The coupling agent (e) contained in the composition (IV) and the protective film-forming film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the coupling agent (e) is used, the content of the coupling agent (e) is preferably 0.03 to 20 parts by mass per 100 parts by mass of the total content of the energy ray-curable component (a) and the acrylic resin (b) in the composition (IV) and the protective film-forming film. By setting the content of the coupling agent (e) to the lower limit or more, effects brought about by the use of the coupling agent (e), such as improvement in dispersibility of the inorganic filler (d) in a resin or improvement in adhesiveness between a protective film-forming film and an adherend, can be more remarkably obtained. By making the content of the coupling agent (e) the upper limit value or less, the generation of outgas (outgas) can be further suppressed.
(crosslinking agent (f))
When a component having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, isocyanate group or the like capable of bonding with other compounds is used as the acrylic resin (b), the composition (IV) and the protective film-forming film may contain the crosslinking agent (f). The crosslinking agent (f) is a component for bonding and crosslinking the functional group in the acrylic resin (b) with another compound, and the initial adhesive force and cohesive force of the protective film forming film can be adjusted by the crosslinking.
Examples of the crosslinking agent (f) include an organic polyisocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent (a crosslinking agent having an aziridine group), and the like.
Examples of the organic polyisocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively abbreviated as "aromatic polyisocyanate compound, etc.); trimers, isocyanurates and adducts of the aromatic polyisocyanate compounds and the like; and isocyanate-terminated urethane prepolymers obtained by reacting the aromatic polyisocyanate compound and 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. Examples of the adduct include xylylene diisocyanate adducts of trimethylolpropane described later. Further, "isocyanate-terminated urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at a molecular terminal portion.
More specifically, the organic polyisocyanate compound includes, for example, 2,4-
Toluene diisocyanate; 2, 6-toluene diisocyanate; 1, 3-xylylene diisocyanate; 1, 4-xylene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-methyl diphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4, 4' -diisocyanate; dicyclohexylmethane-2, 4' -diisocyanate; a compound obtained by adding one or more of toluene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate to all or a part of hydroxyl groups of a polyol such as trimethylolpropane; lysine diisocyanate, and the like.
Examples of the organic polyimine compound include N, N ' -diphenylmethane-4, 4 ' -bis (1-aziridinecarboxamide), trimethylolpropane-tri- β -aziridinylpropionate, tetramethylolmethane-tri- β -aziridinylpropionate, and N, N ' -toluene-2, 4-bis (1-aziridinecarboxamide) triethylenemelamine.
When an organic polyisocyanate compound is used as the crosslinking agent (f), as the acrylic resin (b), a hydroxyl group-containing polymer is preferably used. When the crosslinking agent (f) has an isocyanate group and the acrylic resin (b) has a hydroxyl group, a crosslinked structure can be easily introduced into the protective film-forming film by the reaction of the crosslinking agent (f) with the acrylic resin (b).
The crosslinking agent (f) contained in the composition (IV) and the protective film-forming film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the composition (IV) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the acrylic resin (b). By setting the content of the crosslinking agent (f) to the lower limit or more, the effect by using the crosslinking agent (f) can be more remarkably obtained. By setting the content of the crosslinking agent (f) to the upper limit or less, the excessive use of the crosslinking agent (f) can be suppressed.
(colorant (g))
When the composition (IV) and the protective film-forming film contain the colorant (g), the light transmittance of the protective film-forming film can be adjusted by adjusting the contents thereof. By adjusting the light transmittance in this manner, for example, the visibility of printing when laser printing is performed on the protective film forming film or the protective film can be adjusted. In addition, the design of the protective film can be improved, and the polishing trace on the back surface of the wafer is not easily found.
Examples of the colorant (g) include known colorants such as inorganic pigments, organic pigments, and organic dyes.
Examples of the organic pigments and organic dyes include aminium (aminium) pigments, cyanine pigments, merocyanine pigments, croconium (croconium) pigments, squarylium (squarylium) pigments, azulenium (azulenium) pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalimide (naphthaloctamide) pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex salt pigments), dithiol metal complex pigments, indole pigments, triarylmethane pigments, anthraquinone pigments, naphthol pigments, methine pigments, and methine pigments, Benzimidazolone pigments, pyranthrone pigments, threne pigments and the like.
Examples of the inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (indium tin oxide) pigments, ATO (antimony tin oxide) pigments, and the like.
The colorant (g) contained in the composition (IV) and the protective film-forming film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the colorant (g) is used, the content of the colorant (g) in the composition (IV) and the protective film-forming film may be appropriately selected according to the purpose. For example, as described above, when the printing visibility of the protective film forming film or the protective film, the design of the protective film, or the polishing mark on the back surface of the wafer is improved, or the polishing mark on the back surface of the wafer is not easily found, the content of the colorant (g) in the composition (IV) is preferably 0.05 to 12 mass%, more preferably 0.05 to 9 mass%, and particularly preferably 0.1 to 7 mass% with respect to the total content of all the components except the solvent (i.e., the content of the colorant (g) in the protective film forming film with respect to the total mass of the protective film forming film). By setting the ratio to the lower limit or more, the effect of using the colorant (g) can be more remarkably obtained. By setting the ratio to the upper limit or less, the excessive use of the colorant (g) can be suppressed.
(thermosetting component (h))
When the composition (IV) and the protective film-forming film contain the energy ray-curable component (a) and the thermosetting component (h), the adhesive force to an adherend is increased by heating the protective film-forming film, and the strength of a cured product (for example, a protective film) of the protective film-forming film is also increased.
Examples of the thermosetting component (h) include epoxy thermosetting resins, polyimide resins, unsaturated polyester resins, and the like, and epoxy thermosetting resins are preferable.
The epoxy thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h 2).
The epoxy thermosetting resin contained in the composition (IV) and the protective film-forming film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Epoxy resin (h1)
Examples of the epoxy resin (h1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated products thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, and epoxy resins having a phenylene skeleton.
As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group can be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the chip with the protective film obtained by using the composite sheet for forming a protective film is improved.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a part of epoxy groups of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. The compound can be obtained, for example, by addition reaction of (meth) acrylic acid or a derivative thereof with an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include compounds in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include an ethylene group (vinyl group), a 2-propenyl group (allyl group), (meth) acryloyl group, and (meth) acrylamido group, with acryloyl group being preferred.
The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30000, more preferably 300 to 10000, and particularly preferably 300 to 3000, from the viewpoints of curability of a protective film-forming film and strength and heat resistance of the protective film.
The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000g/eq, more preferably 150 to 950 g/eq.
The epoxy resin (h1) contained in the composition (IV) and the protective film-forming film may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Thermal curing agent (h2)
The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h 1).
Examples of the thermosetting agent (h2) include compounds having two or more functional groups reactive with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group obtained by anhydrizing an acid group, and the like, and a phenolic hydroxyl group, an amino group, or a group obtained by anhydrizing an acid group are preferable, and a phenolic hydroxyl group or an amino group is more preferable.
Examples of the phenolic curing agent having a phenolic hydroxyl group in the thermosetting agent (h2) include polyfunctional phenol resins, biphenol, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins.
Examples of the amine-based curing agent having an amino group in the thermosetting agent (h2) include dicyandiamide and the like.
The heat-curing agent (h2) may have an unsaturated hydrocarbon group.
Examples of the unsaturated hydrocarbon group-containing thermosetting agent (h2) include a compound having a structure in which a part of hydroxyl groups of a phenol resin is substituted with an unsaturated hydrocarbon group, and a compound in which an unsaturated hydrocarbon group is directly bonded to an aromatic ring of a phenol resin.
Examples of the unsaturated hydrocarbon group in the thermosetting agent (h2) include the same groups as those in the unsaturated hydrocarbon group-containing epoxy resin.
When a phenol-based curing agent is used as the thermosetting agent (h2), the thermosetting agent (h2) having a high softening point or glass transition temperature is preferable in terms of improving the peelability of the protective film when peeled from the support sheet.
Among the heat curing agents (h2), for example, the number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolak phenol resin, a dicyclopentadiene phenol resin, an aralkyl phenol resin 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 and dicyandiamide in the thermosetting agent (h2) is not particularly limited, but is preferably 60 to 500, for example.
The heat-curing agent (h2) contained in the composition (IV) and the protective film-forming film may be one type, two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
When the thermosetting component (h) is used, the content of the thermosetting agent (h2) is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the content of the epoxy resin (h1) in the composition (IV) and the protective film-forming film. By setting the content of the thermosetting agent (h2) to the lower limit value or more, curing of the protective film forming film is more easily performed. When the content of the thermosetting agent (h2) is not more than the upper limit, the moisture absorption rate of the protective film forming film decreases, and the reliability of the package obtained by using the chip with the protective film further increases.
When the thermosetting component (h) is used, the content of the thermosetting component (h) (for example, the total content of the epoxy resin (h1) and the thermosetting agent (h 2)) is preferably 5 to 120 parts by mass with respect to 100 parts by mass of the content of the acrylic resin (b) in the composition (IV) and the protective film-forming film. When the content of the thermosetting component (h) is in the above range, for example, the adhesive force between the cured product of the protective film forming film and the supporting sheet is suppressed, and the releasability of the supporting sheet is improved.
(general additive (z))
The general-purpose additive (z) may be any known additive, and may be arbitrarily selected according to the purpose, and is not particularly limited. Examples of the preferable general-purpose additive (z) include a plasticizer, an antistatic agent, an antioxidant, a getter agent, and an ultraviolet absorber.
The composition (IV) and the general-purpose additive (z) contained in the protective film-forming film may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
When the general-purpose additive (z) is used, the content of the general-purpose additive (z) in the composition (IV) and the protective film-forming film is not particularly limited and may be appropriately selected according to the purpose.
For example, when the general-purpose additive (z) is an ultraviolet absorber, in the composition (IV), the proportion of the content of the general-purpose additive (z) (ultraviolet absorber) to the total content of all the components except the solvent (i.e., the proportion of the content of the general-purpose additive (z) (ultraviolet absorber) in the protective film forming film to the total mass of the protective film forming film) is preferably 0.1 to 5% by mass. By setting the ratio to the lower limit or more, the effect by using the general-purpose additive (z) can be more remarkably obtained. By setting the ratio to the upper limit or lower, the excessive use of the general-purpose additive (z) can be suppressed.
(other Polymer (b0) having no energy ray-curable group)
The other polymer (b0) having no energy ray-curable group imparts film-forming property to the protective film.
The polymer (b0) is not particularly limited as long as it is not the acrylic resin (b).
At least a part of the polymer (b0) may be crosslinked by a crosslinking agent, or may not be crosslinked.
Examples of the polymer (b0) include acrylic resins having a weight average molecular weight of greater than 1100000 and acrylic resins having a degree of dispersion of 3.0 or less (these acrylic resins are sometimes referred to as "other acrylic resins" in the present specification); polymers other than acrylic resins having no energy ray-curable group, and the like.
The other acrylic resin may be the same as the acrylic resin (b) except that the acrylic resin has a weight average molecular weight of 1100000 or a dispersity of 3.0 or less.
Examples of the polymer other than the acrylic resin having no energy ray-curable group include urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.
The weight average molecular weight (Mw) of the polymer other than the acrylic resin having no energy ray-curable group is preferably 10000 to 2000000, more preferably 100000 to 1500000, from the viewpoint that the film-forming property of the composition (IV) becomes better.
The polymer (b0) contained in the composition (IV) and the protective film-forming film may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the composition (IV) and the protective film-forming film, the content of the polymer (b0) is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, further preferably 1 part by mass or less, and particularly preferably 0 part by mass, based on 100 parts by mass of the content of the acrylic resin (b), that is, it is particularly preferable that the composition (IV) and the protective film-forming film do not contain the polymer (b 0). By setting the content of the polymer (b0) to the upper limit value or less, the effect of suppressing the peeling of the protective film from the wafer or chip becomes higher.
In the composition (IV), the ratio of the total content of the components that do not belong to the inorganic filler (d) or the solvent to the content of the inorganic filler (d) (that is, the ratio of the total content of the components other than the inorganic filler (d) to the content of the inorganic filler (d) in the protective film-forming film) is 40 mass% or more, preferably 50 mass% or more, and may be, for example, any one of 60 mass% or more and 65 mass% or more. When the ratio is not less than the lower limit value, the effect of suppressing the peeling of the protective film from the wafer or the chip becomes higher.
In the composition (IV), the upper limit value of the ratio of the total content of the components not belonging to the inorganic filler (d) and the solvent to the content of the inorganic filler (d) (that is, the ratio of the total content of the components other than the inorganic filler (d) to the content of the inorganic filler (d) in the protective film forming film) is not particularly limited. The ratio is preferably 90 mass% or less from the viewpoint of well-balanced performance of the property of suppressing peeling of the protective film from the wafer or the chip and the properties other than the property.
In the composition (IV), the ratio of the total content of the components not belonging to the inorganic filler (d) and the solvent to the content of the inorganic filler (d) (that is, the ratio of the total content of the components other than the inorganic filler (d) to the content of the inorganic filler (d) in the protective film forming film) may be appropriately adjusted within a range set by arbitrarily combining any of the lower limit and the upper limit described above. For example, in one embodiment, the ratio is preferably 40 to 90% by mass, more preferably 50 to 90% by mass, and may be in a range of 60 to 90% by mass or 65 to 90% by mass. However, these ranges are only one example of the ratios.
[ solvent ]
The composition (IV) preferably further contains a solvent. The composition (IV) containing a solvent is excellent in handling properties.
The solvent is not particularly limited, but preferable examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The solvent contained in the composition (IV) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
From the viewpoint of enabling the components contained in the composition (IV) to be mixed more uniformly, among the solvents contained in the composition (IV), methyl ethyl ketone and the like are more preferable.
The content of the solvent in the composition (IV) is not particularly limited, and may be appropriately selected depending on the kind of components other than the solvent, for example.
< method for producing composition for forming protective film >)
The energy ray-curable composition for forming a protective film such as composition (IV) can be obtained by blending the components constituting the composition.
The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.
The method for mixing the components at the time of blending is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.
The temperature and time for adding and mixing the components are not particularly limited and may be appropriately adjusted as long as the components are not deteriorated, but the temperature is preferably 15 to 30 ℃.
Fig. 1 is a sectional view schematically showing one example of the protective film forming film of the present embodiment. For the sake of easy understanding of the features of the present invention, important parts of the drawings used in the following description may be enlarged for convenience, and the dimensional ratios of the respective components are not necessarily the same as those in reality.
The protective film forming film 13 shown therein includes a first release film 151 on one surface (sometimes referred to as a "first surface" in this specification) 13a thereof, and a second release film 152 on the other surface (sometimes referred to as a "second surface" in this specification) 13b opposite to the first surface 13 a.
The protective film forming film 13 is suitably stored in a roll form, for example.
The protective film forming film 13 has the above-described characteristics.
The protective film forming film 13 can be formed using the above-described protective film forming composition.
Both the first release film 151 and the second release film 152 may be known release films.
The first release film 151 and the second release film 152 may be the same as each other or different from each other, for example, the release forces required for releasing from the protective film forming film 13 may be different from each other.
In the protective film forming film 13 shown in fig. 1, an exposed surface formed by removing either one of the first release film 151 and the second release film 152 is an attached surface to be attached to the back surface of a wafer (not shown). Next, the exposed surface formed by removing the remaining one of the first release film 151 and the second release film 152 is the attached surface of a support sheet or a dicing sheet to be described later.
In fig. 1, an example is shown in which the release film is provided on both surfaces (the first surface 13a and the second surface 13b) of the protective film forming film 13, but the release film may be provided only on one surface of the protective film forming film 13, that is, only on the first surface 13a or only on the second surface 13 b.
As an example of a preferable protective film forming film of the present embodiment, the following protective film forming films can be cited:
a protective film-forming film which is an energy ray-curable protective film-forming film, wherein,
the protective film forming film contains an acrylic resin (b) having no energy ray-curable group, an energy ray-curable component (a), and an inorganic filler (d),
the weight average molecular weight of the acrylic resin (b) is 1100000 or less, the dispersity is larger than 3.0, the proportion of the total content of the components except the inorganic filler (d) in the protective film forming film to the content of the inorganic filler (d) is more than 40 mass percent,
in the protective film forming film, the content of the acrylic resin (b) is in any range of 8 mass% or more, 10 mass% or more, 12 mass% or more, and 14 mass% or more with respect to the total mass of the protective film forming film,
the content of the energy ray-curable component (a) in the protective film forming film is in any range of 100 to 310 parts by mass, 130 to 280 parts by mass, 130 to 200 parts by mass and 210 to 280 parts by mass relative to 100 parts by mass of the acrylic resin (b),
the content of the inorganic filler (d) in the protective film forming film is within a range of 35 to 75 mass%, 45 to 70 mass%, and 50 to 65 mass% with respect to the total mass of the protective film forming film,
wherein, in the protective film forming film, a ratio of a total content of the acrylic resin (b), the energy ray-curable component (a), and the inorganic filler (d) to a total mass of the protective film forming film is not more than 100 mass%.
As another example of a preferable protective film forming film of the present embodiment, there can be mentioned a protective film forming film,
a protective film-forming film which is an energy ray-curable protective film-forming film, wherein,
the protective film forming film contains an acrylic resin (b) having no energy ray-curable group, an energy ray-curable component (a), and an inorganic filler (d),
the weight average molecular weight of the acrylic resin (b) is 1100000 or less, the dispersity is more than 3.0, the proportion of the total content of the components except the inorganic filler (d) to the content of the inorganic filler (d) in the protective film forming film is more than 40 mass percent,
in the protective film forming film, the content of the acrylic resin (b) is in any range of 8 mass% or more, 10 mass% or more, 12 mass% or more, and 14 mass% or more with respect to the total mass of the protective film forming film,
the content of the energy ray-curable component (a) in the protective film forming film is in any range of 100 to 310 parts by mass, 130 to 280 parts by mass, 130 to 200 parts by mass and 210 to 280 parts by mass relative to 100 parts by mass of the acrylic resin (b),
the content of the inorganic filler (d) in the protective film forming film is within a range of 35 to 75 mass%, 45 to 70 mass%, and 50 to 65 mass% with respect to the total mass of the protective film forming film,
wherein, in the protective film forming film, a ratio of a total content of the acrylic resin (b), the energy ray-curable component (a), and the inorganic filler (d) to a total mass of the protective film forming film is not more than 100 mass%,
holding two sites of a test piece of the protective film forming film having a thickness of 200 μm as a laminate of a plurality of protective film forming films with a space of 20mm, and measuring a storage modulus E ' of the protective film forming film test piece between the two sites in a temperature range of-10 ℃ to 140 ℃ under measurement conditions of a stretching mode with a frequency of 11Hz and a temperature rise rate of 3 ℃/min, wherein the storage modulus E ' of the protective film forming film test piece at 70 ℃ is measured ' 70 Is in any range of 30MPa or less, 10MPa or less and 5MPa or less,
under the illumination of 200mW/cm 2 The light quantity was 300mJ/cm 2 Under the conditions (A), a test piece of a protective film was prepared by irradiating a laminate of a plurality of protective film forming films having a thickness of 50 μm with ultraviolet rays having a wavelength of 365nm twice from each of both sides thereof, respectively, and curing the protective film forming films, holding the test piece of the protective film at two locations with a space of 20mm, and measuring a storage modulus E ' of the test piece of the protective film between the two locations at a temperature range of 0 to 300 ℃ under measurement conditions of a stretching mode having a frequency of 11Hz and a temperature rise rate of 3 ℃/min, and a storage modulus E ' of the test piece of the protective film at 130 ℃ in this case ' 130 Is in any range of 5MPa or more, 8MPa or more, and 10MPa or more.
The protective film forming film of the present embodiment can be attached to the back surface of the wafer so as not to be used together with a support sheet described later. In this case, a release film may be provided on the surface of the protective film forming film opposite to the surface to be bonded to the wafer, and the release film may be removed at an appropriate timing.
On the other hand, by using the protective film forming film of the present embodiment together with a backup sheet described later, a composite sheet for protective film formation can be constituted in which the formation and dicing of the protective film can be performed simultaneously.
Hereinafter, such a composite sheet for forming a protective film will be described.
Diamond compact for forming protective film
The composite sheet for forming a protective film according to an embodiment of the present invention includes a support sheet and a protective film forming film provided on one surface of the support sheet, and the protective film forming film according to the embodiment of the present invention is the above-described protective film forming film.
The composite sheet for forming a protective film according to the present embodiment is provided with the protective film forming film, and thus can suppress the peeling of the protective film from the wafer or chip after the formation of the protective film.
In the present specification, a laminated structure is referred to as a "composite sheet for forming a protective film" even after the protective film forming film is cured, as long as the laminated structure is maintained by maintaining a laminated structure of a support sheet and a cured product of the protective film forming film.
The layers constituting the composite sheet for forming a protective film will be described in detail below.
Supporting piece
The support sheet may be formed of one layer (single layer) or may be formed of a plurality of layers of 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 effect of the present invention is not impaired.
The support sheet is preferably transparent and may be colored according to the purpose.
In the present embodiment in which the protective film forming film has energy ray curability, the support sheet is preferably transmissive to energy rays.
Examples of the support sheet include a support sheet including a base material and an adhesive layer provided on one surface of the base material; a support sheet composed of only a base material, and the like. When the support sheet includes the adhesive layer, the adhesive layer is disposed between the base material and the protective film forming film in the composite sheet for forming a protective film.
When a support sheet including a base material and an adhesive layer is used, in the composite sheet for forming a protective film, the adhesiveness and peelability between the support sheet and the protective film forming film can be easily adjusted.
When a support sheet composed only of a base material is used, a composite sheet for forming a protective film can be manufactured at low cost.
Hereinafter, an example of the composite sheet for forming a protective film according to the present embodiment will be described with reference to the drawings, depending on the type of the support sheet.
Fig. 2 is a sectional view schematically showing an example of the composite sheet for forming a protective film of the present embodiment.
In the drawings subsequent to fig. 2, the same components as those shown in the already-described drawings are denoted by the same reference numerals as those in the already-described drawings, and detailed description thereof will be omitted.
The composite sheet 101 for forming a protective film shown therein is configured by including a support sheet 10 and a protective film forming film 13 provided on one surface (in this specification, sometimes referred to as "first surface") 10a of the support sheet 10.
The support sheet 10 includes a base material 11, and an adhesive layer 12 provided on one surface (first surface) 11a of the base material 11. In the composite sheet 101 for forming a protective film, the adhesive layer 12 is disposed between the base material 11 and the protective film forming film 13.
That is, the composite sheet 101 for forming a protective film is configured by laminating a substrate 11, an adhesive layer 12, and a protective film forming film 13 in this order in the thickness direction thereof.
The first surface 10a of the support sheet 10 is flush with a surface (in this specification, may be referred to as "first surface") 12a of the adhesive layer 12 on the side opposite to the base material 11 side.
The composite sheet 101 for forming a protective film further includes a pressure-sensitive adhesive layer 16 for a jig and a release film 15 on the protective film forming film 13.
In the composite sheet 101 for forming a protective film, the protective film forming film 13 is laminated on the entire or almost entire surface of the first surface 12a of the adhesive agent layer 12, and the adhesive agent layer 16 for a jig is laminated on a part of the surface (in this specification, sometimes referred to as "first surface") 13a of the protective film forming film 13 opposite to the adhesive agent layer 12 side, that is, a region in the vicinity of the peripheral portion. Further, a release film 15 is laminated on a region of the first surface 13a of the protective film forming film 13 where the pressure-sensitive adhesive layer 16 for a jig is not laminated and a surface (in this specification, may be referred to as a "first surface") 16a of the pressure-sensitive adhesive layer 16 for a jig on the side opposite to the protective film forming film 13. The support sheet 10 is provided on a surface (in this specification, sometimes referred to as "second surface") 13b of the protective film forming film 13 on the opposite side to the first surface 13 a.
The composite sheet for forming a protective film of the present embodiment is not limited to the composite sheet 101 for forming a protective film, and the composite sheet for forming a protective film of the present embodiment may have an optional configuration of a release film (for example, the release film 15 shown in fig. 1), and may or may not have a release film.
The jig adhesive layer 16 is used to fix the composite sheet 101 for forming a protective film to a jig such as a ring frame.
The pressure-sensitive adhesive layer 16 for a jig may have, for example, a single-layer structure containing a pressure-sensitive adhesive component, or may have a multilayer structure including a sheet as a core material and pressure-sensitive adhesive component-containing layers provided on both surfaces of the sheet.
As described above, the peeling of the protective film from the wafer or chip after the protective film is formed from the protective film forming film 13 can be suppressed.
The composite sheet 101 for forming a protective film is used in the following manner: in the state where the release film 15 is removed, the back surface of the wafer is attached to the first surface 13a of the protective film forming film 13, and the first surface 16a of the adhesive layer 16 for a jig is further attached to a jig such as a ring frame.
Fig. 3 is a sectional view schematically showing another example of the composite sheet for forming a protective film of the present embodiment.
The composite sheet 102 for forming a protective film shown therein is the same as the composite sheet 101 for forming a protective film shown in fig. 2, except that the shape and size of the protective film forming film are different, and the adhesive layer for a jig is laminated on the first surface of the adhesive layer, not the first surface of the protective film forming film.
More specifically, in the composite sheet for forming a protective film 102, the protective film forming film 23 is laminated on a partial region of the first surface 12a of the adhesive agent layer 12, that is, on a region on the center side in the width direction (the left-right direction in fig. 3) of the adhesive agent layer 12. Further, the pressure-sensitive adhesive layer 16 for a jig is laminated from the outside in the width direction thereof in a region where the protective film forming film 23 is not laminated in the first surface 12a of the adhesive layer 12 so as not to contact the protective film forming film 23 and surround the same. Then, the release film 15 is laminated on a surface (in this specification, it may be referred to as "first surface") 23a of the protective film forming film 23 opposite to the adhesive layer 12 side and a first surface 16a of the jig adhesive layer 16. The support sheet 10 is provided on a surface (in the present specification, sometimes referred to as "second surface") 23b of the protective film forming film 23 on the opposite side to the first surface 23 a.
Fig. 4 is a sectional view schematically showing another example of the composite sheet for forming a protective film of the present embodiment.
The composite sheet 103 for forming a protective film shown therein is the same as the composite sheet 102 for forming a protective film shown in fig. 3, except that it does not include the pressure-sensitive adhesive layer 16 for a jig.
Fig. 5 is a sectional view schematically showing still another example of the composite sheet for forming a protective film of the present embodiment.
The composite sheet 104 for forming a protective film shown therein is the same as the composite sheet 101 for forming a protective film shown in fig. 2, except that it is configured to include the supporting sheet 20 instead of the supporting sheet 10.
That is, the composite sheet 104 for forming a protective film is formed by laminating the substrate 11 and the protective film forming film 13 in the thickness direction thereof.
One surface (surface on the side of the protective film formation film 13, first surface) 20a of the support sheet 20 is the same surface as the first surface 11a of the base material 11.
The substrate 11 has adhesiveness at least on the first surface 11a thereof.
The composite sheet for forming a protective film according to the present embodiment is not limited to the composite sheet for forming a protective film shown in fig. 1 to 5, and may be a composite sheet obtained by modifying or deleting a part of the composite sheet for forming a protective film shown in fig. 1 to 5, or a composite sheet obtained by further adding another configuration to the composite sheet for forming a protective film described above, within a range not to impair the effects of the present invention.
Next, each layer constituting the support sheet will be described in further detail.
O base material
The substrate is in the form of a sheet or a film, and examples of the constituent material include various resins.
Examples of the resin include polyethylene such as Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), and High Density Polyethylene (HDPE); polyolefins other than polyethylene, such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; ethylene copolymers (copolymers obtained using ethylene as a monomer) such as ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, and ethylene-norbornene copolymers; vinyl chloride-based resins (resins obtained using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers; polystyrene; a polycycloolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2, 6-naphthalate, and wholly aromatic polyesters having an aromatic ring group in all the structural units; copolymers of two or more of the above polyesters; poly (meth) acrylates; a polyurethane; a urethane acrylate; a polyimide; a polyamide; a polycarbonate; a fluororesin; a polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfones; polyether ketones, and the like.
Examples of the resin include polymer alloys (polymer alloys) such as a mixture of the polyester and a resin other than the polyester. For the polymer alloy of the polyester with the resin other than it, it is preferable that the amount of the resin other than polyester is smaller.
Examples of the resin include crosslinked resins obtained by crosslinking one or two or more of the above-exemplified resins; modified resins such as ionomers using one or two or more of the above-exemplified resins.
The resin constituting the base material may be one kind only, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The substrate may be composed of one layer (single layer) or a plurality of layers of two or more layers, and when composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
The thickness of the base material is preferably 50 to 300 μm, and more preferably 60 to 100 μm. By setting the thickness of the base material within the above range, the flexibility and the attachment adaptability to the wafer of the composite sheet for forming a protective film are further improved.
The "thickness of the substrate" refers to the thickness of the entire substrate, and for example, the thickness of the substrate composed of a plurality of layers refers to the total thickness of all the layers constituting the substrate.
The base material may contain various known additives such as a filler, a colorant, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent material such as the resin.
The substrate is preferably transparent, and may be colored according to the purpose, and other layers may be deposited.
In the present embodiment in which the protective film-forming film has energy ray curability, the substrate is preferably transmissive to energy rays.
In order to adjust the adhesiveness between the substrate and a layer provided on the substrate (for example, an adhesive layer, a protective film-forming film, or the other layer), the surface may be subjected to an embossing treatment by sandblasting, solvent treatment, or the like; oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment; oleophylic treatment; hydrophilic treatment, etc. In addition, the surface of the substrate may be subjected to a primer treatment.
The substrate may have adhesiveness on at least one surface by containing a component (e.g., a resin or the like) in a specific range.
The substrate can be manufactured by a known method. For example, a resin-containing substrate can be produced by molding a resin composition containing the resin.
Adhesive layer
The adhesive layer is in a sheet or film shape 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.
In the present specification, the "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only a resin having adhesiveness of the resin itself but also a resin exhibiting adhesiveness by being used together with other components such as an additive, a resin exhibiting adhesiveness by the presence of an inducer such as heat or water, and the like.
The adhesive layer may be composed of one layer (single layer) or a plurality of layers of two or more layers, and in the case of being composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 100. mu.m, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
The "thickness of the adhesive agent layer" refers to the thickness of the entire adhesive agent layer, and for example, the thickness of the adhesive agent layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive agent layer.
The adhesive layer is preferably transparent and may be colored according to the purpose.
In the present embodiment in which the protective film-forming film has energy ray curability, the adhesive layer is preferably transmissive to energy rays.
The adhesive layer may be either energy-ray curable or non-energy-ray curable. The energy ray-curable adhesive agent layer can be adjusted in physical properties before and after curing. For example, by curing an energy ray-curable adhesive layer before picking up a chip with a protective film described later, the chip with the protective film can be picked up more easily.
The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive agent layer can be formed at a target site by applying an adhesive agent composition to a surface to be formed of the adhesive agent layer and drying the composition as necessary. The content ratio between the components that do not vaporize at ordinary temperature in the adhesive composition is generally the same as the content ratio between the components in the adhesive layer.
In the adhesive agent layer, the ratio of the total content of one or two or more of the components contained in the adhesive agent layer, which will be described later, to the total mass of the adhesive agent layer is not more than 100 mass%.
Similarly, in the adhesive composition, the ratio of the total content of one or two or more of the components contained in the adhesive composition, which will be described later, to the total mass of the adhesive composition is not more than 100 mass%.
The coating and drying of the adhesive composition can be performed, for example, by the same method as the coating and drying of the above-described composition for forming a protective film.
When the adhesive layer is provided on the substrate, for example, the adhesive composition may be applied to the substrate and dried as necessary. For example, the adhesive layer may be laminated on the substrate by applying an adhesive composition to a release film and drying the adhesive composition as necessary to form an adhesive layer on the release film and bonding an exposed surface of the adhesive layer to one surface of the substrate. The release film in this case may be removed at any time during the production or use of the composite sheet for forming a protective film.
When the adhesive layer is energy ray-curable, examples of the energy ray-curable adhesive composition include an adhesive composition (I-1) containing a non-energy ray-curable adhesive resin (I-1a) (hereinafter, may be abbreviated as "adhesive resin (I-1 a)") and an energy ray-curable compound; an adhesive composition (I-2) comprising an energy ray-curable adhesive resin (I-2a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2 a)") wherein an unsaturated group is introduced into a side chain of a non-energy ray-curable adhesive resin (I-1 a); and an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound.
When the adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable adhesive composition include the adhesive composition (I-4) containing the non-energy ray-curable adhesive resin (I-1 a).
[ non-energy ray-curable adhesive resin (I-1a) ]
The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate.
Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the alkyl group is preferably linear or branched.
The acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate.
Examples of the functional group-containing monomer include a functional group-containing monomer which can form a starting point of crosslinking by reacting the functional group with a crosslinking agent described later, or can introduce an unsaturated group into a side chain of an acrylic polymer by reacting the functional group with a functional group such as an isocyanate group or a glycidyl group in an unsaturated group-containing compound described later.
Examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
The acrylic polymer may further have a structural unit derived from other monomer in addition to a structural unit derived from an alkyl (meth) acrylate and a structural unit derived from a functional group-containing monomer.
The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth) acrylate or the like.
Examples of the other monomer include styrene, α -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.
In the adhesive composition (I-1), the adhesive composition (I-2), the adhesive composition (I-3) and the adhesive composition (I-4) (hereinafter, these adhesive compositions are collectively abbreviated as "adhesive compositions (I-1) to (I-4)"), the acrylic resin such as the acrylic polymer may have only one kind of structural unit, or two or more kinds of structural units, and when two or more kinds of structural units are used, the combination and ratio thereof may be arbitrarily selected.
In the acrylic polymer, the ratio of the amount of the structural unit derived from the functional group-containing monomer to the total amount of the structural units is preferably 1 to 35% by mass.
The adhesive resin (I-1a) contained in the adhesive composition (I-1) or the adhesive composition (I-4) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive agent layer formed of the adhesive agent composition (I-1) or the adhesive agent composition (I-4), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass, for example, may be in any range of 25 to 95% by mass, 45 to 95% by mass, and 65 to 95% by mass, with respect to the total mass of the adhesive agent layer.
[ energy-ray-curable adhesive resin (I-2a) ]
The adhesive resin (I-2a) can be 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 a group capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a), in addition to the energy ray-polymerizable unsaturated group.
Examples of the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (ethylene group), and an allyl group (2-propenyl group), and a (meth) acryloyl group is preferable.
Examples of the group capable of bonding to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group capable of bonding to a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding to a carboxyl group or an epoxy group.
Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate.
The adhesive resin (I-2a) contained in the adhesive composition (I-2) or (I-3) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive layer formed from the adhesive composition (I-2) or (I-3), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass relative to the total mass of the adhesive layer.
[ energy ray-curable Compound ]
Examples of the energy ray-curable compound contained in the adhesive composition (I-1) or (I-3) include a monomer or oligomer having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray.
Examples of the monomer in the energy ray-curable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-
Polyvalent (meth) acrylates such as hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates, and the like.
Examples of the oligomer in the energy ray-curable compound include oligomers of polymers as the above-exemplified monomers.
The energy ray-curable compound contained in the adhesive composition (I-1) or (I-3) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive layer formed from the adhesive composition (I-1) or (I-3), the content of the energy ray-curable compound is preferably 1 to 95% by mass relative to the total mass of the adhesive layer.
[ crosslinking agent ]
When the acrylic polymer further having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), the adhesive composition (I-1) or (I-4) preferably further contains a crosslinking agent.
Further, when the acrylic polymer having a structural unit derived from a functional group-containing monomer, which is, for example, the same as the acrylic polymer in the adhesive resin (I-1a), is used as the adhesive resin (I-2a), the adhesive composition (I-2) or (I-3) may further contain a crosslinking agent.
The crosslinking agent, for example, reacts with the functional groups to crosslink the adhesive resins (I-1a) with each other or to crosslink the adhesive resins (I-2a) with each other.
Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine crosslinking agents (crosslinking agents having an aziridinyl group) such as hexa [1- (2-methyl) -azidinyl ] triphosphatriazine; metal chelate crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelate; an isocyanurate-based crosslinking agent (a crosslinking agent having an isocyanurate skeleton), and the like.
The crosslinking agent contained in the adhesive compositions (I-1) to (I-4) may be one kind only, or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1) or (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, and may be, for example, any one of 1 to 40 parts by mass, 5 to 35 parts by mass, and 10 to 30 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-1 a).
In the adhesive composition (I-2) or (I-3), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ photopolymerization initiator ]
The adhesive compositions (I-1), (I-2) and (I-3) (hereinafter, these adhesive compositions will be collectively referred to as "adhesive compositions (I-1) to (I-3)") may further contain a photopolymerization initiator. The adhesive compositions (I-1) to (I-3) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with a relatively low-energy ray such as ultraviolet ray.
Examples of the photopolymerization initiator include the same photopolymerization initiators as the photopolymerization initiator (c).
The adhesive compositions (I-1) to (I-3) may contain only one kind of photopolymerization initiator, or may contain two or more kinds of photopolymerization initiators, and when the number of kinds of photopolymerization initiators is two or more, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the energy ray-curable compound.
In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound.
[ other additives ]
The adhesive compositions (I-1) to (I-4) may contain other additives not included in any of the above components within a range not impairing the effects of the present embodiment.
Examples of the other additives include known additives such as antistatic agents, antioxidants, softening agents (plasticizers), fillers, rust inhibitors, coloring agents (pigments and dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts).
The reaction retarder is a component that suppresses the occurrence of unintended cross-linking reactions in the adhesive compositions (I-1) to (I-4) during storage, for example, due to the action of the catalyst mixed in the adhesive compositions (I-1) to (I-4). Examples of the reaction retarder include a reaction retarder which forms a chelate complex (chelate complex) by a chelate compound corresponding to a catalyst, and more specifically, a reaction retarder having two or more carbonyl groups (-C (═ O) -) in one molecule.
The other additives contained in the adhesive compositions (I-1) to (I-4) may be only one type, or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
The content of other additives in the adhesive compositions (I-1) to (I-4) is not particularly limited, and may be appropriately selected depending on the kind thereof.
[ solvent ]
The adhesive compositions (I-1) to (I-4) may contain a solvent. By adding the solvents to the adhesive compositions (I-1) to (I-4), the coating suitability to the surface to be coated is improved.
The solvent is preferably an organic solvent, and examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.
The adhesive compositions (I-1) to (I-4) may contain only one solvent, or may contain two or more solvents, and when two or more solvents are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the solvent in the adhesive compositions (I-1) to (I-4) is not particularly limited, and may be appropriately adjusted.
Method for preparing O adhesive composition
The adhesive compositions such as the adhesive compositions (I-1) to (I-4) can be obtained by blending the adhesive with components other than the adhesive, which are blended as necessary, for each component constituting the adhesive composition.
The adhesive composition can be prepared, for example, by the same method as the above-described composition for forming a protective film, except that the kind of blending component is different.
Manufacturing method of composite sheet for protective film formation
The composite sheet for forming a protective film can be produced by laminating the above layers so that the layers are in a corresponding positional relationship, and adjusting the shape of part or all of the layers as necessary. The formation method of each layer is as described above.
For example, when an adhesive layer is laminated on a substrate in the production of a support sheet, the adhesive composition may be applied to the substrate and dried as necessary.
In addition, the adhesive layer can be laminated on the substrate by a method in which the adhesive composition is applied to the release film and dried as necessary to form the adhesive layer on the release film and the exposed surface of the adhesive layer is bonded to one surface of the substrate. In this case, the pressure-sensitive adhesive composition is preferably applied to the release-treated surface of the release film.
The case where an adhesive agent layer is laminated on a substrate has been exemplified so far, but the above-described method can be applied to, for example, a case where a layer other than the adhesive agent layer is laminated on a substrate.
On the other hand, for example, when a protective film forming film is further laminated on an adhesive layer laminated on a substrate, a protective film forming composition can be applied on the adhesive layer to directly form a protective film forming film. A layer other than the protective film forming film can also be laminated on the adhesive layer in the same manner using the composition for forming the layer. Thus, when a new layer (hereinafter, simply referred to as "second layer") is formed on any one of the layers already laminated on the base material (hereinafter, simply referred to as "first layer") to form a continuous two-layer laminated structure (in other words, a laminated structure of the first layer and the second layer), a method of coating the composition for forming the second layer on the first layer and drying it as necessary can be applied.
The second layer is preferably formed on a release film in advance using a composition for forming the layer, and an exposed surface of the formed second layer on the side opposite to the side in contact with the release film is bonded to an exposed surface of the first layer to form a continuous two-layer laminated structure. In this case, the composition is preferably applied to the release-treated surface of the release film. After the laminated structure is formed, the release film may be removed as necessary.
However, the target laminated structure can be arbitrarily selected, for example, a laminated structure in a case where a layer (film) other than the protective film forming film is laminated on the adhesive agent layer.
In this manner, since the layers other than the base material constituting the composite sheet for forming a protective film can be laminated by a method of forming the layers on the release film in advance and bonding the layers to the surface of the target layer, the composite sheet for forming a protective film can be produced by appropriately selecting the layers in the above steps as necessary.
The composite sheet for forming a protective film is usually stored in a state where a release film is bonded to the surface of the outermost layer (for example, a protective film forming film) on the side opposite to the support sheet of the composite sheet for forming a protective film. Therefore, by applying a composition for forming the outermost layer, such as a composition for forming a protective film, to the release film (preferably, the release-treated surface thereof) and drying it as necessary, the outermost layer is formed on the release film, and by any of the above methods, the remaining layers are laminated on the exposed surface of the layer on the side opposite to the side in contact with the release film, and the release film is bonded without removing the release film, whereby a composite sheet for forming a protective film with a release film can be obtained.
Manufacturing method of chip with protective film (protective film forming film and use method of composite sheet for protective film formation)
The protective film-forming film and the protective film-forming composite sheet are useful for the production of the chip with a protective film.
That is, a method for manufacturing a chip with a protective film according to an embodiment of the present invention is a method for manufacturing a chip with a protective film including a chip and a protective film provided on a back surface of the chip, the method including: a step (which may be referred to as "bonding step" in this specification) of bonding the protective film forming film according to the embodiment of the present invention to the back surface of a wafer to prepare a first laminated film in which the protective film forming film and the wafer are laminated in the thickness direction thereof, or bonding the protective film forming film of the composite sheet for forming a protective film according to the embodiment of the present invention to the back surface of a wafer to prepare a first laminated composite sheet in which the support sheet, the protective film forming film and the wafer are laminated in this order in the thickness direction thereof; a step (which may be referred to as a "curing step" in the present specification) of forming the protective film by energy ray curing the protective film-forming film in the first laminated film or the first laminated composite sheet, and producing a second laminated film formed by laminating the protective film and the wafer in the thickness direction thereof, or producing a second laminated composite sheet formed by laminating the backup sheet, the protective film, and the wafer in this order in the thickness direction thereof; a step (which may be referred to as a "dividing step" in this specification) of dividing the wafer in the second laminated film and cutting the protective film in a state where a dicing sheet is provided on the protective film side of the second laminated film to produce a third laminated film in which a plurality of chips with protective films are fixed to the dicing sheet, or dividing the wafer in the second laminated composite sheet and cutting the protective film to produce a third laminated composite sheet in which a plurality of chips with protective films are fixed to the support sheet; and a step of picking up the chip with the protective film by pulling the chip with the protective film in the third laminated composite film away from the dicing sheet or pulling the chip with the protective film in the third laminated composite sheet away from the support sheet (in this specification, it may be referred to as a "picking-up step").
Hereinafter, a method for manufacturing a chip with a protective film (hereinafter, referred to as "manufacturing method 1" in some cases) when a protective film forming film that does not form a composite sheet for forming a protective film is attached to the back surface of a wafer, and a method for manufacturing a chip with a protective film (hereinafter, referred to as "manufacturing method 2" in some cases) when a protective film forming film in a composite sheet for forming a protective film is attached to the back surface of a wafer will be described in order with reference to the drawings.
< manufacturing method 1>
Fig. 6A to 6E are sectional views for schematically explaining the manufacturing method 1. The manufacturing method 1 will be described, taking as an example the case of forming the film 13 using the protective film shown in fig. 1.
In the sticking step of the manufacturing method 1, as shown in fig. 6A, the protective film forming film 13 is stuck to the back surface 9b of the wafer 9, thereby manufacturing a first laminated film 601 in which the protective film forming film 13 and the wafer 9 are laminated in the thickness direction thereof. A first surface 13a of a protective film forming film 13 is attached to the back surface 9b of the wafer 9. The second peeling film 152 is provided on the second face 13b of the protective film forming film 13.
Here, the case where the first release film 151 is removed from the protective film forming film 13 shown in fig. 1 and the first surface 13a of the protective film forming film 13 is attached to the back surface 9b of the wafer 9 is shown, but the second release film 152 may be removed from the protective film forming film 13 shown in fig. 1 and the second surface 13b of the protective film forming film 13 is attached to the back surface 9b of the wafer 9.
The protective film forming film 13 can be attached to the wafer 9 by a known method. For example, the protective film forming film 13 may be attached to the wafer 9 while being heated.
Next, in the curing step of the manufacturing method 1, the protective film 13 'is formed by curing the protective film forming film 13 in the first laminated film 601 with an energy ray, and thereby a second laminated film 602 in which the protective film 13' and the wafer 9 are laminated in the thickness direction thereof is manufactured as shown in fig. 6B. The symbol 13a 'denotes a surface of the protective film 13' that has once been the first surface 13a of the protective film forming film 13 (in this specification, sometimes referred to as "first surface"). Symbol 13b 'represents a protective film 13'
The surface (in this specification, sometimes referred to as "second surface") that once serves as the second surface 13b of the protective film forming film 13.
In the curing step, the protective film 13' is formed by irradiating the protective film forming film 13 with energy rays from the outside of the first laminate film 601 on the protective film forming film 13 side through the second release film 152 (through the second release film 152).
In the curing step, the protective film 13' may be formed by removing the second release film 152 from the protective film forming film 13 of the first laminate film 601 to expose the second surface 13b of the protective film forming film 13 and then irradiating the protective film forming film 13 with energy rays.
The irradiation conditions of the energy ray in the curing step are as described above.
By forming the film 13 using the protective film, the protective film 13' can be suppressed from being peeled off from the wafer 9 in the second laminated film 602 obtained by the curing step.
Next, in the dividing step of the manufacturing method 1, first, the second release film 152 is removed from the protective film 13' in the second laminated film 602. Then, as shown in fig. 6C, one surface (in this specification, it may be referred to as "first surface") 8a of the dicing sheet 8 is attached to the second surface 13b 'of the protective film 13' newly exposed thereby.
The dicing sheet 8 shown here is configured to include a base material 81 and an adhesive layer 82 provided on one surface 81a of the base material 81, and the adhesive layer 82 in the dicing sheet 8 is attached to the protective film 13'. The surface (in this specification, sometimes referred to as "first surface") 82a of the adhesive layer 82 on the protective film 13' side is the same as the first surface 8a of the dicing sheet 8.
The dicing sheet 8 may be a known dicing sheet. For example, the substrate 81 may be the same substrate as that in the protective film-forming composite sheet, and the adhesive layer 82 may be the same adhesive layer as that in the protective film-forming composite sheet. That is, the dicing sheet 8 may be the same sheet as the support sheet in the composite sheet for forming a protective film.
Here, although the dicing sheet 8 including the base material 81 and the adhesive agent layer 82 is used, a sheet other than this may be used as the dicing sheet in the dividing step, and for example, a dicing sheet composed only of the base material may be used.
Next, in the dividing step, as shown in fig. 6D, the wafer 9 in the second laminated film 602 is divided and the protective film 13 'is cut in a state where the dicing sheet 8 is provided on the protective film 13' side of the second laminated film 602. The wafer 9 is divided into individual chips 90.
The wafer 9 may be divided and the protective film 13' may be cut by a known method. The wafer 9 and the protective film 13' can be continuously divided by various dicing such as blade dicing, laser dicing by laser irradiation, or water dicing by jetting water containing an abrasive.
In any of the cutting methods, the protective film 13' is cut along the outer periphery of the chip 90.
Thus, by dividing the wafer 9 and cutting the protective film 13 ', a plurality of protective film-attached chips 901 can be obtained, and the protective film (hereinafter, simply referred to as "protective film") 130' provided on the rear surface 90b of the chip 90 and the chip 90 after cutting is provided on the protective film 901. The reference numeral 130b 'denotes a surface (in this specification, may be referred to as a "second surface") of the cut protective film 130', which is the second surface 13b 'of the protective film 13'.
In the dividing step of the manufacturing method 1, the third laminated film 603 in which the plurality of chips 901 with protective films are fixed to the dicing sheet 8 is manufactured in the above manner.
By forming the protective film 13, the protective film 13 'can be prevented from being peeled off from the wafer 9 before and during dicing, and the protective film 130' can be prevented from being peeled off from the chip 90, during a period from when the dicing process is started to when the third laminated film 603 is obtained.
Next, in the pickup step of the manufacturing method 1, as shown in fig. 6E, the chip 901 with the protective film in the third laminate film 603 is pulled away from the dicing sheet 8, and the chip 901 with the protective film is picked up.
In the pickup step, peeling occurs between the second surface 130b 'of the protective film 130' in the protective film-attached chip 901 and the first surface 82a of the adhesive agent layer 82 in the dicing sheet 8.
Here, a case where the chip 901 with the protective film is pulled off in the direction of the arrow P using a pulling-off tool 7 such as a vacuum nozzle (vacuum collet) is shown. In addition, the cross-sectional view of the pull-off tool 7 is omitted here.
The chip 901 with the protective film can be picked up by a known method.
When the adhesive agent layer 82 is energy ray-curable, it is preferable that, in the pickup step, the adhesive agent layer 82 is irradiated with an energy ray to cure the adhesive agent layer 82 to form a cured product (not shown), and then the chip 901 with the protective film is pulled off from the dicing sheet 8. At this time, in the pickup step, the protective film 130' in the chip 901 with a protective film and the cured product of the adhesive layer 82 in the dicing sheet 8 are peeled off from each other.
In this case, since the adhesion between the cured product of the adhesive layer 82 and the protective film 130 'is smaller than the adhesion between the adhesive layer 82 and the protective film 130', the chip 901 with the protective film can be picked up more easily.
The irradiation conditions for irradiating the adhesive agent layer 82 with energy rays in the pickup step may be the same as the irradiation conditions for irradiating the protective film forming film 13 with energy rays in the curing step, for example.
In the present specification, if a laminated structure of a substrate and a cured product of an energy ray-curable adhesive agent layer is maintained, the laminated structure is referred to as a "dicing sheet" even after the energy ray-curable adhesive agent layer is cured by an energy ray.
On the other hand, when the adhesive agent layer 82 is non-energy ray-curable, the chip 901 with the protective film may be pulled off directly from the adhesive agent layer 82, and curing of the adhesive agent layer 82 is not necessary, so that the chip 901 with the protective film can be picked up in a simplified process.
Even if the adhesive agent layer 82 is energy ray curable, the chip 901 with the protective film can be picked up by a simplified process without curing the adhesive agent layer 82.
In the pickup step, the pickup of the protective film-attached chip 901 can be performed for all the target protective film-attached chips 901.
By using the protective film forming film 13, the protective film 130' can be prevented from peeling off from the chip 90 during the period from the start to the end of the pickup process, both before and after the pickup.
In the manufacturing method 1, the chip 901 with the protective film can be obtained as a target by performing the pickup step.
The case where the first laminated film is produced, then the protective film is formed by energy ray curing the protective film forming film in the first laminated film, the second laminated film is produced, and then the dicing sheet is attached to the protective film in the second laminated film, the wafer is divided, and the protective film is cut has been described. That is, the case where the curing step is performed after the attaching step, and then the dicing sheet is attached to the attachment object (here, the protective film), and then the dividing step is performed will be described. However, in the manufacturing method 1, the timing of attaching the dicing sheet to the attachment object is not limited to this.
For example, in the manufacturing method 1, after the first laminated film is manufactured, a dicing sheet may be attached to the protective film forming film in the first laminated film, the protective film forming film in the first laminated film with a dicing sheet (in some cases, the first laminated film with a support sheet) thus obtained may be cured with an energy ray to form a protective film, a second laminated film may be manufactured, and the wafer in the second laminated film may be divided to cut the protective film. That is, after the sticking step, the dicing sheet may be stuck to the object to be stuck (here, the protective film forming film), and the curing step may be performed on the first laminate film with the dicing sheet (in some cases, the first laminate film with the support sheet) obtained by the sticking step, and then the dividing step may be performed. The first laminated film with the supporting sheet is the same as the first laminated composite sheet described later. Fig. 7A to 7E are sectional views schematically illustrating the manufacturing method 1 in this case.
< manufacturing method 2>
Fig. 8A to 8D are sectional views for schematically explaining the manufacturing method 2. The production method 2 will be described by taking, as an example, a case where the composite sheet 101 for forming a protective film shown in fig. 2 is used.
In the sticking step of the production method 2, as shown in fig. 8A, the protective film forming film 13 of the protective film forming composite sheet 101 is stuck to the back surface 9b of the wafer 9, whereby a first laminated composite sheet 501 is produced in which the support sheet 10, the protective film forming film 13, and the wafer 9 are laminated in this order in the thickness direction thereof. In this case, the first surface 13a of the protective film forming film 13 in the protective film forming composite sheet 101 is attached to the back surface 9b of the wafer 9 in the same manner as in the manufacturing method 1.
The protective film forming film 13 in the protective film forming composite sheet 101 can be attached to the wafer 9 by a known method. For example, the protective film forming film 13 may be attached to the wafer 9 while being heated.
Next, in the curing step of the production method 2, the protective film 13 'is formed by energy ray curing the protective film forming film 13 in the first laminated composite sheet 501, and as shown in fig. 8B, a second laminated composite sheet 502 is produced which is formed by laminating the support sheet 10, the protective film 13' and the wafer 9 in this order in the thickness direction thereof.
In the curing step, the protective film 13' is formed by irradiating the protective film forming film 13 with an energy ray from the outside of the first laminated composite sheet 501 on the support sheet 10 side through the support sheet 10 (through the support sheet 10).
The curing step can be performed by the same method as the curing step in the manufacturing method 1, except that the first laminated composite sheet 501 is used instead of the first laminated film 601.
The second laminated composite sheet 502 obtained in the curing step has the same configuration as the laminate of the second laminated film 602 and the dicing sheet 8 in the dividing step of the manufacturing method 1. When the cutting sheet 8 is the same as the support sheet 10, the second laminated composite sheet 502 is the same as the laminate.
By using the protective film forming film 13, the protective film 13' can be prevented from being peeled off from the wafer 9 in the second laminated composite sheet 502 obtained in the curing step.
Next, in the dividing step of the manufacturing method 2, as shown in fig. 8C, the wafer 9 in the second laminated composite sheet 502 is divided, and the protective film 13' is cut. The wafer 9 is singulated by the dicing into a plurality of chips 90.
The dividing step may be performed in the same manner as the dividing step in the manufacturing method 1, except that the second laminated composite sheet 502 is used instead of the laminate of the second laminated film 602 and the dicing sheet 8.
In the manufacturing method 2, the protective film 13' is cut along the outer periphery of the chip 90 regardless of the cutting method.
Thus, by dividing the wafer 9 and cutting the protective film 13 ', a plurality of chips 901 with protective films can be obtained, and the chips 901 with protective films include the chips 90 and the cut protective films 130' provided on the back surfaces 90b of the chips 90.
These chips 901 with protective films obtained in the dividing step of manufacturing method 2 are the same as the chips 901 with protective films obtained in the dividing step of manufacturing method 1.
As described above, in the dividing step of the manufacturing method 2, the third laminated composite sheet 503 is manufactured, which is configured by fixing the plurality of chips 901 with the protective film to the support sheet 10.
The third laminated composite sheet 503 has the same configuration as the third laminated film 603 obtained in the dividing step of the production method 1. When the cut sheet 8 is the same as the support sheet 10, the third laminated composite sheet 503 is the same as the third laminated film 603.
By using the protective film forming film 13, the protective film 13 'can be prevented from being peeled off from the wafer 9 before and during the dicing process and the protective film 130' can be prevented from being peeled off from the chip 90 during the period from the start of the dicing process to the time when the third laminated composite sheet 503 is obtained.
Next, in the pickup step of the manufacturing method 2, as shown in fig. 8D, the chip 901 with the protective film in the third laminated composite sheet 503 is pulled away from the support sheet 10, and the chip 901 with the protective film is picked up.
In the pickup step, the separation occurs between the second surface 130b 'of the protective film 130' in the chip with protective film 901 and the first surface 12a of the adhesive agent layer 12 in the support sheet 10.
The pickup process may be performed by the same method as the pickup process in the manufacturing method 1, except that the third laminated composite sheet 503 is used instead of the third laminated film 603.
For example, when the adhesive layer 12 is energy-ray curable, in the pickup step, it is preferable that the adhesive layer 12 is irradiated with an energy ray to cure the adhesive layer 12 to form a cured product (not shown), and then the chip 901 with the protective film is pulled off from the support sheet 10. At this time, in the pickup step, the protective film 130' of the chip 901 with a protective film is peeled off from the cured product of the adhesive layer 12 of the support sheet 10.
In this case, since the adhesion between the cured product of the adhesive layer 12 and the protective film 130 'is smaller than the adhesion between the adhesive layer 12 and the protective film 130', the chip 901 with the protective film can be picked up more easily.
On the other hand, when the adhesive layer 12 is non-energy ray-curable, the chip 901 with the protective film may be pulled off directly from the adhesive layer 12, and curing of the adhesive layer 12 is not necessary, so that the chip 901 with the protective film can be picked up in a simplified process.
Even if the adhesive layer 12 is energy ray curable, the chip 901 with the protective film can be picked up by a simplified process without curing the adhesive layer 12.
By using the protective film forming film 13, the protective film 130' can be prevented from peeling off from the chip 90 during the period from the start to the end of the pickup process, both before and after the pickup.
In the manufacturing method 2, the chip 901 with a protective film can be obtained as a target by performing the pickup step. The chip with a protective film 901 obtained in production method 2 is the same as the chip with a protective film 901 obtained in production method 1.
The production method 2 in the case of using the composite sheet 101 for forming a protective film shown in fig. 2 has been described, but in the production method 2, a composite sheet 102 for forming a protective film, a composite sheet 103 for forming a protective film, a composite sheet 104 for forming a protective film shown in fig. 3 to 5, or the composite sheet 101 for forming a protective film of the present embodiment other than the composite sheet 101 for forming a protective film may be used.
Manufacturing method of substrate apparatus (method of using chip with protective film)
After the chip with the protective film is obtained by the above-described manufacturing method, the substrate apparatus can be manufactured by the same method as the manufacturing method of the conventional substrate apparatus, except that the chip with the protective film is used instead of the conventional chip with the protective film.
As a method for manufacturing the substrate device, for example, there is a manufacturing method including a flip chip connection step of electrically connecting the bump electrodes and the connection pads on the circuit board by bringing the bump electrodes on the chip with the protective film, which is formed by using the protective film, into contact with the connection pads on the circuit board.
By forming a film using the protective film of the present embodiment, the protective film can be suppressed from being peeled off from the chip in the substrate device. Therefore, the substrate device is superior to the conventional substrate device in terms of high reliability.
Examples
The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited to the examples shown below.
< raw materials for production of resin >
The following are formal names of raw materials for preparing resins abbreviated in examples and comparative examples.
MA: acrylic acid methyl ester
HEA: 2-Hydroxyethyl acrylate
2 EHMA: 2-ethylhexyl methacrylate
< raw Material for production of composition for Forming protective film >
The raw materials used for preparing the composition for forming a protective film are shown below.
[ energy ray-curable component (a) ]
(a) -1: urethane acrylate (Quick cure 8100EA70 manufactured by KJ Chemicals Corporation)
(a) -2: epsilon-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate ("A-9300-1 CL" manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., 3-functional ultraviolet-curable Compound)
[ acrylic resin (b) having no energy ray-curable group ]
(b) -1: an acrylic resin (weight average molecular weight 400000, dispersity 4.0, glass transition temperature 6 ℃) which is a copolymer of MA (85 parts by mass) and HEA (15 parts by mass).
(b) -2: an acrylic resin (weight average molecular weight 400000, dispersity 3.1, glass transition temperature 6 ℃) which is a copolymer of MA (85 parts by mass) and HEA (15 parts by mass).
(b) -3: an acrylic resin (weight average molecular weight 700000, dispersity 3.6, glass transition temperature 6 ℃) which is a copolymer of MA (85 parts by mass) and HEA (15 parts by mass).
(b) -4: an acrylic resin (weight average molecular weight 900000, dispersity of 4.0, glass transition temperature of 6 ℃) which is a copolymer of MA (85 parts by mass) and HEA (15 parts by mass).
(b) -5: an acrylic resin (weight average molecular weight 900000, dispersity of 3.1, glass transition temperature of 6 ℃) which is a copolymer of MA (85 parts by mass) and HEA (15 parts by mass).
[ photopolymerization initiator (c) ]
(c) -1: 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (Omnirad (registered trade Mark) 369, manufactured by BASF corporation)
(c) -2: 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one (Omnirad (registered trademark) 127D, manufactured by BASF corporation)
[ inorganic Filler (d) ]
(d) -1: silica filler (fused silica filler, average particle diameter 8 μm)
[ colorant (g) ]
(g) -1: a black Pigment (a Pigment obtained by mixing 32 parts by mass of a phthalocyanine-based Blue Pigment (Pigment Blue 15:3), 18 parts by mass of an isoindolinone-based Yellow Pigment (Pigment Yellow 139), and 50 parts by mass of an anthraquinone-based Red Pigment (Pigment Red 177) to prepare a Pigment so that the total amount of the three pigments/the amount of the styrene acrylic resin is 1/3 (mass ratio))
[ general additive (z) ]
(z) -1: hydroxyphenyltriazine ultraviolet absorber ("Tinuvin (registered trademark) 479" manufactured by BASF corporation)
[ other Polymer (b0) having no energy ray-curable group ]
(b0) -1: an acrylic resin (weight average molecular weight 1300000, dispersity 4.0, glass transition temperature 6 ℃) which is a copolymer of MA (85 parts by mass) and HEA (15 parts by mass).
(b0) -2: an acrylic resin (weight average molecular weight 900000, dispersity of 2.0, glass transition temperature of 6 ℃) which is a copolymer of MA (85 parts by mass) and HEA (15 parts by mass).
(b0) -3: an acrylic resin (weight average molecular weight 400000, dispersity 2.0, glass transition temperature 6 ℃) which is a copolymer of MA (85 parts by mass) and HEA (15 parts by mass).
< production of protective film-forming film, composite sheet for protective film formation, and chip with protective film >
[ example 1]
< preparation of composition (IV) -1 for Forming protective film >
Energy ray-curable composition (IV) -1 for forming an energy ray-curable protective film having a total concentration of all components except the solvent of 45 mass% was obtained by dissolving or dispersing energy ray-curable component (a) -1(10.1 mass parts), energy ray-curable component (a) -2(12.4 mass parts), acrylic resin (b) -1(14.7 mass parts) having no energy ray-curable group, photopolymerization initiator (c) -1(0.1 mass part), photopolymerization initiator (c) -2(0.5 mass part), inorganic filler (d) -1(58.4 mass parts), colorant (g) -1(3 mass parts), and general-purpose additive (z) -1(0.8 mass part) in methyl ethyl ketone and stirring at 23 ℃. The amounts of the components other than the solvent described herein are the amounts of the target compound without solvent.
< production of protective film-forming film >
The above-obtained composition (IV) -1 for forming a protective film was coated on the release-treated surface thereof using a release film (second release film, "SP-PET 382150" manufactured by linetec Corporation, having a thickness of 38 μm) obtained by subjecting one surface of a polyethylene terephthalate film to a release treatment by a silicone treatment, and dried at 100 ℃ for 2 minutes, thereby producing an energy ray-curable protective film forming film having a thickness of 25 μm.
Further, a release-treated surface of a release film (first release film, "SP-PET 381031" manufactured by linec Corporation, having a thickness of 38 μm) was bonded to an exposed surface of the obtained protective film forming film on the side not having the second release film, thereby obtaining a protective film forming film with a release film, which was configured by having a protective film forming film, a first release film provided on one surface of the protective film forming film, and a second release film provided on the other surface of the protective film forming film.
< preparation of adhesive composition (I-4) -1 >
A non-energy ray-curable adhesive composition (I-4) -1 containing an acrylic resin (100 parts by mass), a toluene diisocyanate-based crosslinking agent ("BHS 8515" manufactured by ltd.) (10 parts by mass in terms of a crosslinking agent component), a hexamethylene diisocyanate-based crosslinking agent ("CORONATE HL" manufactured by Tosoh Corporation) (7.5 parts by mass in terms of a crosslinking agent component), and further containing methyl ethyl ketone as a solvent was prepared. The acrylic resin was a copolymer having a weight average molecular weight of 600000, which was obtained by copolymerizing 2EHMA (80 parts by mass) and HEA (20 parts by mass).
< production of supporting sheet >
The release film (SP-PET 381031 manufactured by LINTEC Corporation, 38 μm thick) obtained by subjecting one surface of a polyethylene terephthalate film to a release treatment by a silicone treatment was used, and the obtained adhesive composition (I-4) -1 was applied to the release-treated surface thereof, followed by heating and drying at 100 ℃ for 2 minutes, thereby forming a non-energy ray-curable adhesive layer having a thickness of 5 μm.
Then, a polypropylene film (80 μm thick, colorless) as a base material was laminated on the exposed surface of the adhesive layer, thereby producing a support sheet with a release film, which was formed by laminating the base material, the adhesive layer, and the release film in this order in the thickness direction thereof.
< production of chip with protective film >
The first release film and the second release film were removed from the protective film forming film obtained above using a tape bonding apparatus ("advill RAD-3600F/12" manufactured by LINTEC Corporation), and one newly produced exposed surface of the protective film forming film was thermally laminated on a #2000 polished surface of an 8-inch silicon wafer (thickness 350 μm) under conditions of an attachment temperature of 70 ℃, an attachment pressure of 0.3MPa, and an attachment speed of 50 mm/sec, thereby bonding the protective film forming film to the silicon wafer (attachment step). Thereby producing a first laminated film.
The release film was removed from the support sheet obtained above. Then, the first laminated film fixed to the apparatus was fixed to the ring frame using a tape application apparatus ("Adwill RAD-2700" manufactured by LINTEC Corporation). Then, the exposed surface of the adhesive layer produced by removing the release film and the exposed surface of the protective film forming film were laminated under conditions of an adhesion pressure of 0.3MPa and an adhesion speed of 20 mm/sec, and the support sheet was adhered to the protective film forming film in the first laminated film (adhesion step). Thereby producing a first laminate film with a support sheet.
Next, for the first laminated film with the support sheet, an ultraviolet irradiation device ("RAD" manufactured by LINTEC Corporation) was used2000 m/8'), with an illumination of 200mW/cm 2 The light quantity was 300mJ/cm 2 And (3) irradiating the protective film-forming film with ultraviolet rays twice through the base material and the adhesive layer to cure the protective film-forming film and form the protective film (curing step). Thereby producing a second laminated film.
Next, the second laminated film was cut with a blade using a dicing apparatus ("DFD 6362" manufactured by DISCO Corporation) to divide the silicon wafer into silicon chips having a size of 3mm × 3mm, and the protective film was cut along the outer periphery of the silicon chips to produce a plurality of chips with the protective film (dividing step). Thus, a third laminated film was produced in which a plurality of silicon chips with protective films were fixed to a support sheet. These silicon chips with the protective film were dried together with the chips at 125 ℃ for 24 hours.
Next, the silicon chip with the protective film in the third laminate film is pulled away from the support sheet, and the silicon chip with the protective film is picked up (pickup step).
Thus, the target chip with the protective film was obtained.
[ example 2]
< preparation of composition (IV) -2 for Forming protective film >
A protective film forming composition (IV) -2 was prepared in the same manner as the protective film forming composition (IV) -1 in example 1, except that the acrylic resin (b) -2 having no energy ray-curable group (14.7 parts by mass) was used in place of the acrylic resin (b) -1 having no energy ray-curable group (14.7 parts by mass).
< production of protective film-forming film and chip with protective film >
A protective film-forming film was produced in the same manner as in example 1, except that the protective film-forming composition (IV) -2 was used in place of the protective film-forming composition (IV) -1.
Next, a chip with a protective film was produced in the same manner as in example 1, except that the protective film was used to form a film.
[ example 3]
< preparation of composition (IV) -3 for Forming protective film >
A protective film forming composition (IV) -3 was prepared in the same manner as the protective film forming composition (IV) -1 in example 1, except that the acrylic resin (b) -3 having no energy ray-curable group (14.7 parts by mass) was used in place of the acrylic resin (b) -1 having no energy ray-curable group (14.7 parts by mass).
< production of protective film-forming film and chip with protective film >
A protective film-forming film was produced in the same manner as in example 1, except that the protective film-forming composition (IV) -3 was used in place of the protective film-forming composition (IV) -1.
Next, a chip with a protective film was produced in the same manner as in example 1, except that the protective film was used to form a film.
[ example 4]
< preparation of composition (IV) -4 for Forming protective film >
A protective film forming composition (IV) -4 was prepared in the same manner as the protective film forming composition (IV) -1 in example 1, except that the acrylic resin (b) -4 having no energy ray-curable group (14.7 parts by mass) was used in place of the acrylic resin (b) -1 having no energy ray-curable group (14.7 parts by mass).
< production of protective film-forming film and chip with protective film >
A protective film-forming film was produced in the same manner as in example 1, except that the protective film-forming composition (IV) -4 was used in place of the protective film-forming composition (IV) -1.
Next, a chip with a protective film was produced in the same manner as in example 1, except that the protective film was used to form a film.
[ example 5]
< preparation of composition (IV) -5 for Forming protective film >
A protective film forming composition (IV) -5 was prepared in the same manner as the protective film forming composition (IV) -1 in example 1, except that the acrylic resin (b) -5(14.7 parts by mass) having no energy ray-curable group was used in place of the acrylic resin (b) -1(14.7 parts by mass) having no energy ray-curable group.
< production of protective film-forming film and chip with protective film >
A protective film forming film was produced in the same manner as in example 1, except that the protective film forming composition (IV) -5 was used instead of the protective film forming composition (IV) -1.
Next, a chip with a protective film was produced in the same manner as in example 1, except that the protective film was used to form a film.
Comparative example 1
< preparation of composition (X) -1 for Forming protective film >
A protective film forming composition (X) -1 was prepared in the same manner as the protective film forming composition (IV) -1 in example 1, except that another polymer (b0) -1(14.7 parts by mass) having no energy ray-curable group was used in place of the acrylic resin (b) -1(14.7 parts by mass) having no energy ray-curable group.
< production of protective film-forming film and chip with protective film >
A protective film-forming film was produced in the same manner as in example 1, except that the protective film-forming composition (X) -1 was used in place of the protective film-forming composition (IV) -1.
Next, a chip with a protective film was manufactured in the same manner as in example 1, except that the protective film was used to form a film.
Comparative example 2
< preparation of composition (X) -2 for Forming protective film >
A protective film forming composition (X) -2 was prepared in the same manner as the protective film forming composition (IV) -1 in example 1, except that the other polymer (b0) -2(14.7 parts by mass) having no energy ray-curable group was used in place of the acrylic resin (b) -1(14.7 parts by mass) having no energy ray-curable group.
< production of protective film-forming film and chip with protective film >
A protective film-forming film was produced in the same manner as in example 1, except that the protective film-forming composition (X) -2 was used in place of the protective film-forming composition (IV) -1.
Next, a chip with a protective film was produced in the same manner as in example 1, except that the protective film was used to form a film.
Comparative example 3
< preparation of composition (X) -3 for Forming protective film >
A protective film forming composition (X) -3 was prepared in the same manner as the protective film forming composition (IV) -1 in example 1, except that the other polymer (b0) -3(14.7 parts by mass) having no energy ray-curable group was used in place of the acrylic resin (b) -1(14.7 parts by mass) having no energy ray-curable group.
< production of protective film-forming film and chip with protective film >
A protective film-forming film was produced in the same manner as in example 1, except that the protective film-forming composition (X) -3 was used in place of the protective film-forming composition (IV) -1.
Next, a chip with a protective film was manufactured in the same manner as in example 1, except that the protective film was used to form a film.
Comparative example 4
< preparation of composition (X) -4 for Forming protective film >
A protective film forming composition (X) -4 was prepared in the same manner as in the protective film forming composition (IV) -1 of example 1 except that the amount of the energy ray-curable component (a) -1 was changed to 5 parts by mass instead of 10.1 parts by mass, the amount of the energy ray-curable component (a) -2 was changed to 6.6 parts by mass instead of 12.4 parts by mass, the amount of the acrylic resin (b) -5(10 parts by mass) having no energy ray-curable group was changed to 14.7 parts by mass instead of the acrylic resin (b) -1 having no energy ray-curable group, the amount of the inorganic filler (d) -1 was changed to 75 parts by mass instead of 58.4 parts by mass, and the amount of the colorant (g) -1 was changed to 2 parts by mass instead of 3 parts by mass.
< production of protective film-forming film and chip with protective film >
A protective film forming film was produced in the same manner as in example 1, except that the protective film forming composition (X) -4 was used instead of the protective film forming composition (IV) -1.
Next, a chip with a protective film was produced in the same manner as in example 1, except that the protective film was used to form a film.
Comparative example 5
< preparation of composition (X) -5 for Forming protective film >
A protective film-forming composition (X) -5 was prepared in the same manner as in the protective film-forming composition (IV) -1 in example 1 except that the amount of the energy ray-curable component (a) -1 was changed to 5 parts by mass instead of 10.1 parts by mass, the amount of the energy ray-curable component (a) -2 was changed to 6.6 parts by mass instead of 12.4 parts by mass, the amount of the acrylic resin (b) -1 having no energy ray-curable group was changed to 10 parts by mass instead of 14.7 parts by mass, the amount of the inorganic filler (d) -1 was changed to 75 parts by mass instead of 58.4 parts by mass, and the amount of the colorant (g) -1 was changed to 2 parts by mass instead of 3 parts by mass.
< production of protective film-forming film and chip with protective film >
A protective film-forming film was produced in the same manner as in example 1, except that the protective film-forming composition (X) -5 was used in place of the protective film-forming composition (IV) -1.
Next, a chip with a protective film was manufactured in the same manner as in example 1, except that the protective film was used to form a film.
< evaluation of protective film formation film >
< evaluation of protective film peeling inhibition Effect >
In each of examples and comparative examples, a total of 25 silicon chips with a protective film obtained as described above were stored for 7 days while being left to stand in an environment at a temperature of 85 ℃ and a relative humidity of 85%. Subsequently, the silicon chip with the protective film after storage was subjected to heat treatment at 260 ℃ for 10 minutes in a reflow furnace.
Further, the 25 silicon chips with the protective film after the heat treatment were subjected to the following temperature cycle test: the cooling-heating procedure was repeated 1000 times in total of cooling at-40 ℃ for 10 minutes and then heating at 125 ℃ for 10 minutes.
Then, it was confirmed that the number N (N is an integer of 0 to 25) of silicon chips with a protective film, from which the protective film was not peeled off from the silicon chips, was found in 25 silicon chips with a protective film after the temperature cycle test by using an SAT apparatus ("D9600 CSAM" manufactured by SONO SCAN, inc.). Next, the peeling inhibiting effect of the protective film was evaluated according to the following criteria. The results are shown in table 1 or table 2. The corresponding columns in tables 1 and 2 are collectively referred to as "N/25".
A: n is 25.
B: n is 23 to 24.
C: n is 22 or less.
The description of "-" in the column of the component contained in tables 1 and 2 means that the protective film forming film does not contain the component.
< measurement of storage modulus of protective film formation film >
In each of examples and comparative examples, a plurality of protective film forming films with release films obtained as described above were used, and the first release film or the second release film was removed and exposed surfaces of the protective film forming films were bonded to each other, thereby producing a test piece (protective film forming film test piece) which was a laminate of the plurality of protective film forming films (thickness was 200 μm, and length in the stretching direction in the stretching mode described later was 30 mm).
Next, the storage modulus E' of the test piece of the protective film-forming film was measured in a temperature range of-10 ℃ to 140 ℃ under conditions of constant temperature rise of a tensile method (tensile mode), an inter-chuck distance of 20mm, an Amplitude of 5 μm, a frequency of 11Hz, and a temperature rise rate of 3 ℃/min using an automatic dynamic viscoelasticity measuring apparatus ("RHEOVBRON DDV-01 FP" manufactured by A & D Company, Limited).
< measurement of storage modulus of protective film >
In each of examples and comparative examples, a plurality of protective film formation films with release films obtained as described above were used, and the exposed surfaces of the protective film formation films were bonded to each other while removing the first release film or the second release film, thereby producing a laminate (thickness 50 μm) of the plurality of protective film formation films.
Next, an ultraviolet irradiation apparatus ("RAD 2000 m/8" manufactured by LINTEC Corporation) was used to irradiate light at an illuminance of 200mW/cm 2 The light quantity was 300mJ/cm 2 And irradiating the laminate with ultraviolet rays twice from both sides thereof, respectively, to cure the protective film-forming film, thereby forming a protective film. After a laminate of a plurality of protective films was obtained in the above manner, a test piece (protective film test piece) (thickness 50 μm, length in the stretching direction in the stretching mode described later was 30mm) was produced by making the width thereof 5 mm.
Next, the storage modulus E' of the protective film test piece was measured in a temperature range of 0 ℃ to 300 ℃ under the conditions of measurement of constant temperature rise of a tensile method (tensile mode) with an inter-chuck distance of 20mm, an Amplitude of 5 μm, a frequency of 11Hz, and a temperature rise rate of 3 ℃/min using a dynamic mechanical analyzer ("DMA Q800" manufactured by TA Instruments).
[ Table 1]
[ Table 2]
From the above results, it is understood that the peeling of the protective film from the silicon chip is remarkably suppressed in examples 1 to 5, and that the effect is high in examples 1 to 4 in particular.
The protective film forming films of examples 1 to 5 contained the acrylic resin (b) having a weight average molecular weight of 900000 or less and a dispersity of 3.1 or more and the inorganic filler (d), and the ratio of the total content of the components other than the inorganic filler (d) to the content of the inorganic filler (d) in these protective film forming films was 71.2 mass%.
Storage modulus E 'of protective film forming film test piece at 70℃' 70 Is 0.8MPa (example 1)) 0.9MPa (example 2), 0.9MPa (example 3), 1.4MPa (example 4), and 1.6MPa (example 5) have excellent characteristics in terms of attachment to a wafer. In addition, in the silicon chips with the protective films of examples 1 to 5, a void portion was not substantially formed between the protective film and the silicon chip, and the adhesion between the protective film and the silicon chip was high.
Storage modulus E 'of the protective film test piece at 130℃' 130 46MPa (example 1), 48MPa (example 2), 47MPa (example 3), 54MPa (example 4) and 61MPa (example 5), and all had excellent characteristics as a protective film.
However, in comparative examples 1 to 5, the effect of suppressing the peeling of the protective film from the silicon chip was low, and in particular, in comparative example 4, the effect was low.
The protective film forming films of comparative examples 4 and 5 contained the acrylic resin (b) having a weight average molecular weight of 900000 and a dispersity of 3.1 or more and the inorganic filler (d), but the ratio of the total content of the components other than the inorganic filler (d) to the content of the inorganic filler (d) in these protective film forming films was 33.3% by mass.
The protective film-forming films of comparative examples 1 to 3 do not contain the acrylic resin (b) and instead contain another polymer (b0) having no energy ray-curable group. In the other polymer (b0), the weight average molecular weight of the other polymer (b0) -1 (comparative example 1) was 1300000, and the degree of dispersion of the other polymer (b0) -2 (comparative example 2) and the other polymer (b0) -3 (comparative example 3) was 2.0.
Industrial applicability
The present invention can be used for manufacturing various substrate devices including semiconductor devices.
Claims (4)
1. A protective film-forming film which is an energy ray-curable protective film-forming film, wherein,
the protective film forming film contains an acrylic resin (b) having no energy ray-curable group and an inorganic filler (d),
the weight average molecular weight of the acrylic resin (b) is less than 1100000, the dispersity is more than 3.0,
in the protective film forming film, the ratio of the total content of the components other than the inorganic filler (d) to the content of the inorganic filler (d) is 40 mass% or more.
2. The protective film forming film according to claim 1, further comprising a polyfunctional urethane (meth) acrylate oligomer as the energy ray-curable component (a).
3. A composite sheet for forming a protective film, which comprises a support sheet and a protective film forming film provided on one surface of the support sheet,
the protective film forming film is the protective film forming film described in claim 1 or 2.
4. A method for manufacturing a chip with a protective film, which includes a chip and a protective film provided on a back surface of the chip, wherein the method for manufacturing the chip with the protective film includes:
a step of producing a first laminated film in which the protective film forming film according to claim 1 or 2 is attached to the back surface of a wafer and the protective film forming film and the wafer are laminated in the thickness direction thereof, or producing a first laminated composite sheet in which the protective film forming composite sheet according to claim 3 is attached to the back surface of a wafer and the support sheet, the protective film forming film and the wafer are laminated in the thickness direction thereof in this order;
a step of forming the protective film by energy ray curing the protective film forming film in the first laminated film or the first laminated composite sheet, thereby producing a second laminated film formed by laminating the protective film and the wafer in the thickness direction thereof, or producing a second laminated composite sheet formed by laminating the support sheet, the protective film, and the wafer in this order in the thickness direction thereof;
a step of producing a third laminated film in which a plurality of chips with a protective film are fixed to a dicing sheet by dividing the wafer in the second laminated film and cutting the protective film in a state in which the dicing sheet is provided on the protective film side of the second laminated film, or producing a third laminated composite sheet in which a plurality of chips with a protective film are fixed to the supporting sheet by dividing the wafer in the second laminated composite sheet and cutting the protective film; and
and picking up the chip with the protective film by pulling the chip with the protective film in the third laminated film away from the cutting sheet or pulling the chip with the protective film in the third laminated composite sheet away from the support sheet.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-055012 | 2021-03-29 | ||
| JP2021055012A JP2022152295A (en) | 2021-03-29 | 2021-03-29 | Protective film formation film, composite sheet for forming protective film, and method for manufacturing chip with protective film |
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| Publication Number | Publication Date |
|---|---|
| CN115124743A true CN115124743A (en) | 2022-09-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210072759.5A Pending CN115124743A (en) | 2021-03-29 | 2022-01-21 | Protective film forming film, composite sheet for forming protective film, and method for producing chip with protective film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2022152295A (en) |
| KR (1) | KR20220135155A (en) |
| CN (1) | CN115124743A (en) |
| TW (1) | TW202239923A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7241022B2 (en) | 2017-10-27 | 2023-03-16 | リンテック株式会社 | Film for forming protective film, composite sheet for forming protective film, and method for producing semiconductor chip |
-
2021
- 2021-03-29 JP JP2021055012A patent/JP2022152295A/en active Pending
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2022
- 2022-01-21 KR KR1020220009515A patent/KR20220135155A/en unknown
- 2022-01-21 CN CN202210072759.5A patent/CN115124743A/en active Pending
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| Publication number | Publication date |
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| JP2022152295A (en) | 2022-10-12 |
| TW202239923A (en) | 2022-10-16 |
| KR20220135155A (en) | 2022-10-06 |
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