Protective film forming film, composite sheet for forming protective film, and method for manufacturing chip with protective film

Abstract

The present application provides a kind of protective film forming film, which is energy ray curable protective film forming film, the protective film forming film contains acrylic resin (b) without energy ray curable group, the acrylic resin (b) has the structural unit derived from 4- (methyl) acryloyl morpholine, in the acrylic resin (b), the proportion of the amount of the structural unit derived from 4- (methyl) acryloyl morpholine relative to the total amount of structural unit is 10 mass% or more, in the protective film forming film, the proportion of the content of the acrylic resin (b) relative to the total mass of the protective film forming film is 8 mass% or more.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a protective film forming film, a composite sheet for forming a protective film, and a chip with a protective film. This application claims priority based on Japanese Patent Application No. 2021-055011 filed in Japan on March 29, 2021, the contents of which are incorporated herein by reference. Background Technology

[0002] Among wafers such as semiconductor wafers or insulator wafers, there exists a type of wafer in which circuitry is formed on one side (circuit surface) and further has protruding electrodes such as bumps on that side (circuit surface). Such a wafer can be diced to form a chip and can be mounted on a circuit substrate by connecting its protruding electrodes to connection pads on the circuit substrate. In such wafers or chips, in order to prevent damage such as cracks, a protective film is sometimes used to protect the side (back side) opposite to the circuit surface.

[0003] To form such a protective film, a protective film forming film is attached to the back side of the wafer. Sometimes the protective film forming film is laminated on a support sheet to support it, forming a protective film forming composite; sometimes it is not laminated on the support sheet. Next, the wafer with the protective film forming film on its back side is processed into a chip with a protective film on its back side (a chip with a protective film) through various subsequent processes. This chip with a protective film is then picked up and mounted on a circuit board to form various substrate devices (e.g., semiconductor devices).

[0004] In protective film formation, there exists a type of non-curable protective film that functions as a protective film in its original state without curing. When using a non-curable protective film, since a curing process is unnecessary, chips with protective films can be manufactured at low cost through a simplified method. On the other hand, when using a curable protective film, since the cured product serves as the protective film, it offers the advantage of high wafer protection performance. Furthermore, thermosetting protective films cured by heating require a long heating time during curing, while energy-curable protective films cured by energy radiation have the advantage of completing the energy radiation irradiation for curing in a short time. Therefore, various energy-curable protective films are being developed (see Patent Document 1). Existing technical documents Patent documents

[0005] Patent Document 1: International Publication No. 2019 / 082959 Summary of the Invention The technical problem to be solved by the present invention

[0006] However, regardless of whether the protective film is curable, it is possible for it to peel off from the wafer or chip after it is applied to the back of the wafer and until it is finally used to construct various substrate devices. For example, the protective film may peel off from the wafer or chip when dicing the wafer into chips, cutting the protective film to chip size, picking up chips with protective films, and in the substrate device. Even when the protective film is curable, it is possible for it to peel off from the wafer or chip during curing. Therefore, its practicality would be even greater if this peeling could be suppressed in the energy-curable protective film formation.

[0007] The present invention aims to provide a protective film forming film, a protective film forming composite sheet having 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, wherein the protective film forming film is an energy-curable protective film forming film, which can suppress the protective film from peeling off from the wafer or chip after the protective film is formed by the protective film forming film attached to the wafer. Technical means to solve technical problems

[0008] This invention provides a protective film forming film, which is an energy-curable protective film forming film. The protective film forming film contains an acrylic resin (b) without energy-curable groups. The acrylic resin (b) has structural units derived from 4-(meth)acryloylmorpholine. In the acrylic resin (b), the amount of the 4-(meth)acryloylmorpholine-derived structural units relative to the total amount of structural units is 10% by mass or more. In the protective film forming film, the content of the acrylic resin (b) relative to the total mass of the protective film forming film is 8% by mass or more.

[0009] In the protective film forming film of the present invention, the content of the acrylic resin (b) relative to the total mass of the protective film forming film can be less than 25% by mass. The protective film forming film of the present invention may further contain a multifunctional urethane (meth)acrylate oligomer as an energy ray curable component (a).

[0010] The present invention provides a composite sheet for forming a protective film, which includes a support sheet and a protective film forming film disposed on one side of the support sheet, wherein the protective film forming film is the protective film forming film of the present invention described above. This invention provides a method for manufacturing a chip with a protective film. The method comprises the following steps: firstly, a first laminated film is formed by attaching the protective film forming film of the present invention to the back of a wafer, stacking the protective film forming film and the wafer along their thickness directions; or secondly, a first laminated composite film is formed by attaching the protective film forming film of the present invention to the back of a wafer, stacking the support sheet, the protective film forming film, and the wafer sequentially along their thickness directions; and thirdly, a protective film is formed by energy-curing the protective film forming film in the first laminated film or the first laminated composite film, stacking the protective film and the wafer along their thickness directions. The process includes: a second laminated film formed by stacking layers, or a second laminated composite film formed by sequentially stacking the support sheet, protective film, and wafer along their thickness directions; a third laminated film formed by dividing the wafer in the second laminated film and cutting the protective film with a dicing blade provided on the protective film side, thereby forming a third laminated composite film with multiple chips with protective films fixed on the dicing blade; or a third laminated composite film formed by dividing the wafer in the second laminated composite film and cutting the protective film, thereby forming a third laminated composite film with multiple chips with protective films fixed on the support sheet; and a pickup process by pulling the chips with protective films from the dicing blade or from the support sheet in the third laminated composite film. Invention Effects

[0011] According to the present invention, a method for manufacturing a protective film forming film, a protective film forming composite sheet having the protective film forming film, and a chip with a protective film using the protective film forming film or the protective film forming composite sheet is provided, wherein the protective film forming film is an energy-curable protective film forming film, which can suppress the protective film from peeling off from the wafer or chip after the protective film is formed by the protective film forming film attached to the wafer. Attached Figure Description

[0012] Figure 1 A cross-sectional view illustrating an example of a protective film forming film according to one embodiment of the present invention. Figure 2 A cross-sectional view illustrating an example of a composite sheet for forming a protective film according to one embodiment of the present invention. Figure 3 A cross-sectional view illustrating another example of a composite sheet for forming a protective film according to one embodiment of the present invention. Figure 4A cross-sectional view illustrating another example of a composite sheet for forming a protective film according to one embodiment of the present invention. Figure 5 A cross-sectional view illustrating another example of a composite sheet for forming a protective film according to one embodiment of the present invention. Figure 6A This is a cross-sectional view illustrating an example of a method for manufacturing a chip with a protective film according to one embodiment of the present invention. Figure 6B This is a cross-sectional view illustrating an example of a method for manufacturing a chip with a protective film, representing one embodiment of the present invention. Figure 6C This is a cross-sectional view illustrating an example of a method for manufacturing a chip with a protective film according to one embodiment of the present invention. Figure 6D This is a cross-sectional view illustrating an example of a method for manufacturing a chip with a protective film according to one embodiment of the present invention. Figure 6E This is a cross-sectional view illustrating an example of a method for manufacturing a chip with a protective film, representing one embodiment of the present invention. Figure 7A This is a cross-sectional view illustrating another example of a method for manufacturing a chip with a protective film, which is used to schematically explain one embodiment of the present invention. Figure 7B This is a cross-sectional view illustrating another example of a method for manufacturing a chip with a protective film, which is used to schematically explain one embodiment of the present invention. Figure 7C This is a cross-sectional view illustrating another example of a method for manufacturing a chip with a protective film, which is used to schematically explain one embodiment of the present invention. Figure 7D This is a cross-sectional view illustrating another example of a method for manufacturing a chip with a protective film, which is used to schematically explain one embodiment of the present invention. Figure 7E This is a cross-sectional view illustrating another example of a method for manufacturing a chip with a protective film, which is used to schematically explain one embodiment of the present invention. Figure 8A This is a cross-sectional view illustrating yet another example of a method for manufacturing a chip with a protective film, which is used to schematically explain one embodiment of the present invention. Figure 8B This is a cross-sectional view illustrating yet another example of a method for manufacturing a chip with a protective film, which is used to schematically explain one embodiment of the present invention. Figure 8C This is a cross-sectional view illustrating yet another example of a method for manufacturing a chip with a protective film, which is used to schematically explain one embodiment of the present invention. Figure 8D This is a cross-sectional view illustrating yet another example of a method for manufacturing a chip with a protective film, which is used to schematically explain one embodiment of the present invention. Explanation of reference numerals in the attached figures 10, 20: Support sheet; 10a, 20a: One side (first side) of the support sheet; 11: Substrate; 12: Adhesive layer; 13, 23: Protective film forming film (energy-curable protective film forming film); 13': Protective film; 13b': The other side (second side) of the protective film; 130': Cut protective film; 101, 102, 103, 104: Composite sheet for forming protective film; 501: First laminated composite sheet; 502: Second laminated composite sheet; 503: Third laminated composite sheet; 601: First laminated film; 602: Second laminated film; 603: Third laminated film; 8: Cutting sheet; 9: Wafer; 9b: Back side of wafer; 90: Chip; 90b: Back side of chip; 901: Chip with protective film. Detailed Implementation

[0013] ◇ Protective film formation In one embodiment of the present invention, the protective film forming film is energy-curable. The protective film forming film contains an acrylic resin (b) (sometimes referred to simply as "acrylic resin (b)") that does not have energy-curable groups. The acrylic resin (b) has structural units derived from 4-(meth)acryloylmorpholine. In the acrylic resin (b), the amount of the 4-(meth)acryloylmorpholine-derived structural units is 10% by mass or more relative to the total amount of structural units. In the protective film forming film, the content of the acrylic resin (b) is 8% by mass or more relative to the total mass of the protective film forming film. The protective film forming film in this embodiment is a film used to protect the chip by setting a protective film on the chip.

[0014] By using the protective film forming film of this embodiment or a composite sheet for forming a protective film having the protective film forming film of this embodiment, it is possible to manufacture a chip having a chip and a protective film disposed on the back of the chip. The chip with the protective film can be manufactured, for example, by attaching a protective film to the back of the wafer to form a protective film, curing the protective film to form a protective film, dividing the wafer into chips, and cutting the protective film along the outer periphery of the chips.

[0015] In this specification, the term "wafer" may include semiconductor wafers made of elemental semiconductors such as silicon, germanium, and selenium, or compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; and insulator wafers made of insulators such as sapphire and glass. Circuits are formed on one side of these wafers. In this specification, this side of the wafer with the circuit formed is referred to as the "circuit side". The side of the wafer opposite to the circuit side is referred to as the "back side". Wafers are divided into chips through dicing and other methods. In this specification, as with wafers, the side of the chip where the circuitry is formed is called the "circuit side", and the side of the chip opposite to the circuit side is called the "back side". Both the circuit surfaces of the wafer and the chip have protruding electrodes such as bumps and pillars. These protruding electrodes are preferably made of solder.

[0016] Furthermore, by using the chip with the protective film, a substrate device can be manufactured. In this specification, "substrate device" refers to a device in which a chip with a protective film is connected to bonding pads on a circuit substrate in a flip-chip manner at the protruding electrodes on its circuit surface. For example, if a semiconductor wafer is used as the wafer, a semiconductor device can be listed as a substrate device.

[0017] The protective film forming film of this embodiment contains a specific amount or more of the acrylic resin (b) and the acrylic resin (b) has a specific amount or more of structural units derived from 4-(meth)acryloylmorpholine, which can suppress the protective film from peeling off from the wafer or chip after the protective film is formed by curing the protective film forming film attached to the wafer.

[0018] In this specification, "(meth)acryloyl" is a concept that includes both "acryloyl" and "methacryloyl", and "4-(meth)acryloylmorpholine" is a concept that includes both "4-acryloylmorpholine" and "4-methacryloylmorpholine". Similarly, similar terms include, for example, "(meth)acrylic acid" which includes both "acrylic acid" and "methacrylic acid", and "(meth)acrylate" which includes both "acrylate" and "methacrylate".

[0019] Because 4-(meth)acryloylmorpholine has higher polarity than other conventional monomers, acrylic resin (b) containing a certain amount or more of structural units derived from 4-(meth)acryloylmorpholine exhibits higher polarity than other conventional acrylic resins and other resins derived from 4-(meth)acryloylmorpholine. It is presumed that the protective film forming film of this embodiment achieves the aforementioned superior effects by containing the aforementioned acrylic resin (b).

[0020] The protective film formed in this embodiment is energy-curable by radiation, and may further be thermosetting, or not thermosetting. When the protective film formed in this embodiment has both energy-curable and thermosetting properties, the contribution of energy-curing to the formation of the protective film is greater than that of thermosetting.

[0021] In this specification, "energy rays" refers to rays containing energy quanta within electromagnetic waves or beams of charged particles. Examples of energy rays include ultraviolet light, radiation, and electron beams. For instance, ultraviolet light can be irradiated using a high-pressure mercury lamp, fusion lamp, xenon lamp, black light, or LED light as an ultraviolet source. As for electron beams, electron beams generated using electron beam accelerators or similar devices can be used. In this specification, "energy-ray curing property" refers to the property of curing by irradiation with energy rays, and "non-energy-ray curing property" refers to the property of not curing even when irradiated with energy rays. Furthermore, "non-curing" refers to the property that does not cure regardless of any means such as heating or irradiation with energy rays.

[0022] As long as the degree of curing is sufficient to allow the protective film to fully perform its function, there are no particular limitations on the curing conditions when the protective film is formed by energy ray curing. The curing conditions can be appropriately selected according to the type of protective film. For example, the irradiance of the energy rays used to cure the protective film formed by energy rays is preferably 60–320 mW / cm². 2 Furthermore, the intensity of the energy rays during curing is preferably 100–1000 mJ / cm². 2 .

[0023] The protective film forming film preferably contains the acrylic resin (b) and other components besides the acrylic resin (b). Examples of protective film forming films include those containing an energy-curable component (a) and the acrylic resin (b) (an acrylic resin (b) without energy-curable groups). The components of the protective film forming the film will be described in detail later.

[0024] Preferably, the protective film forming membrane satisfies the following conditions for energy storage modulus E'. That is, a test piece of a 200 μm thick protective film forming film (sometimes referred to simply as a "protective film forming film test piece" in this specification) is held at two points with a 20 mm gap, and the storage modulus E' of the protective film forming film test piece is measured between the two points under the following conditions: a tensile mode with a frequency of 11 Hz, a heating rate of 3 °C / min, and a temperature range of -10 °C to 140 °C. The storage modulus E' of the protective film forming film test piece at 70 °C is then measured. 70 Preferably, it is 30 MPa or less, more preferably 10 MPa or less, and for example, it can be 5 MPa or less. This is achieved by making the energy storage modulus E'... 70 Below the aforementioned upper limit value, it is easier to apply a protective film to the object to be attached (wafer). The energy storage modulus E' 70 There is no specific lower limit. For example, the energy storage modulus E' 70 Protective films with a strength of 0.5 MPa or higher are easier to manufacture, resulting in protective films with better properties. In this specification, “thickness” is not limited to the test piece. Unless otherwise specified, it refers to the average thickness measured at 5 randomly selected locations on the object, which can be obtained using a constant pressure thickness gauge according to JIS K7130.

[0025] Provided that the accuracy of the energy storage modulus E' is not compromised, the length of the protective film forming test piece in the tensile direction under the tensile mode is not particularly limited, but is preferably 30 mm or more. When determining the storage modulus E' of the protective film forming test piece, it is preferable to heat the test piece at a constant rate. When determining the storage modulus E' of the protective film forming test piece, the amplitude is preferably 5 μm.

[0026] The protective film that forms the energy-cured protective film preferably satisfies the following conditions for energy storage modulus E'. That is, at an illuminance of 200 mW / cm² 2 The light intensity is 300 mJ / cm² 2Under certain conditions, a multi-layer protective film with a thickness of 50 μm was irradiated twice from each side with ultraviolet light at a wavelength of 365 nm, thereby curing the protective film and producing a protective film test piece (sometimes referred to simply as a "protective film test piece" in this specification). The test piece was held at two points with a 20 mm gap between them, and the storage modulus E' of the protective film test piece was measured between these two points under the following conditions: a tensile mode with a frequency of 11 Hz, a heating rate of 3 °C / min, and a temperature range of 0 °C to 300 °C. The storage modulus E' of the protective film test piece at 130 °C was then measured. 130 Preferably, it is 5 MPa or higher, more preferably 8 MPa or higher, and even more preferably 10 MPa or higher. This is achieved by increasing the energy storage modulus E'. 130 When the value is above the lower limit, the protective effect of the protective film on the attached object (wafer) becomes higher. The energy storage modulus E' 130 There is no specific upper limit. For example, the energy storage modulus E' 130 Protective films with pressures below 3000MPa are easier to manufacture and have better properties.

[0027] As long as the accuracy of the energy storage modulus E' is not compromised, the length of the protective film test piece in the tensile direction under the tensile mode is not particularly limited, but is preferably 30 mm or more. When determining the storage modulus E' of the protective film test piece, it is preferable to heat the test piece at a constant rate. When determining the storage modulus E' of the protective film test piece, the amplitude is preferably 5 μm.

[0028] 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, for example, by adjusting the types and contents of the components contained in the protective film forming composition described later, particularly the acrylic resin (b) without energy-curable groups, the energy-curable component (a), etc. For example, by increasing the content of low molecular weight components, such as the energy-curable component (a) described later, in the protective film forming film, the storage modulus E' of the protective film forming film test piece can be reduced. Furthermore, by increasing the content of the inorganic filler material (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-curable component (a) described later in the protective film forming film, the storage modulus E' of the protective film test piece can be increased. Furthermore, by reducing the content of the inorganic filler material (d) described later in the protective film forming film, the storage modulus E' of the protective film test piece can also be increased.

[0029] The protective film can consist of a single layer or multiple layers. When the protective film consists of multiple layers, these layers can be the same as each other or different from each other, and there are no particular restrictions on the combination of these multiple layers.

[0030] In this specification, the term "multiple layers" is not limited to the protective film forming the film. "Multiple layers may be the same as each other or different from each other" means that "all layers may be the same, all layers may be different, or only some layers may be the same." Furthermore, "multiple layers may be different from each other" means that "at least one of the constituent materials and thicknesses of each layer is different from each other."

[0031] The thickness of the protective film is preferably 1–100 μm, more preferably 3–80 μm, and particularly preferably 5–60 μm. By making the thickness of the protective film above or below the lower limit, a protective film with higher protective performance can be formed. By making the thickness of the protective film below or below the upper limit, the thickness of the chip with the protective film can be prevented from becoming too thick. The “thickness of the protective film forming membrane” refers to the overall thickness of the protective film forming membrane. For example, the thickness of a protective film forming membrane composed of multiple layers refers to the total thickness of all the layers that make up the protective film forming membrane.

[0032] <<Composition for forming protective film>> The protective film forming film can be formed using an energy-curable protective film forming composition (sometimes referred to simply as "protective film forming composition") containing the constituent materials of the protective film forming film. For example, the protective film forming film can be formed by coating the protective film forming composition onto the surface to which it is to be formed and drying it as needed. The content ratio of the components in the protective film forming composition that do not vaporize at room temperature is generally the same as the content ratio of the components in the protective film forming film. In this specification, "room temperature" refers to a temperature at which no special cooling or heating is required, i.e., a normal temperature, such as temperatures of 18 to 28°C.

[0033] In the protective film forming membrane, the total content of one or more of the components described below in the protective film forming membrane is no more than 100% by mass relative to the total mass of the protective film forming membrane. Similarly, in the protective film forming composition, the total content of one or more of the components described below in the protective film forming composition is not greater than 100 by mass relative to the total mass of the protective film forming composition.

[0034] The coating of the protective film forming composition can be carried out using known methods, such as air knife coating machines, scraper coating machines, bar coating machines, gravure coating machines, roller coating machines, roller knife coating machines, screen coating machines, die coating machines, doctor blade coating machines, screen coaters, Mayer bar coating machines, kiss coaters, and other coating machines.

[0035] There are no particular limitations on the drying conditions of the protective film forming composition. However, when the protective film forming composition contains the solvent described later, it is preferable to heat-dry it. Furthermore, for example, it is preferable to heat-dry the solvent-containing protective film forming composition at 70–130°C for 10 seconds to 5 minutes. However, for thermosetting protective film forming compositions, it is preferable to heat-dry the composition itself and the thermosetting protective film formed from it without thermal curing.

[0036] <Composition for forming protective films that can be cured by energy rays (IV)> Preferred compositions for forming protective films include, for example, an acrylic resin (b) containing the aforementioned group that does not have an energy-curable group, and an energy-curable protective film forming composition (IV) containing the energy-curable component (a) (in this specification, it is sometimes simply referred to as "composition (IV)").

[0037] [Acrylic resin without energy-curing groups (b)] The acrylic resin (b) is a component used to impart film-forming properties to the protective film and to inhibit the peeling of the protective film from the wafer or chip.

[0038] The acrylic resin (b) has structural units derived from 4-(meth)acryloylmorpholine. That is, the acrylic resin (b) is a polymer of 4-(meth)acryloylmorpholine. Preferably, the acrylic resin (b) has structural units derived from 4-(meth)acryloylmorpholine and other structural units. That is, the acrylic resin (b) is preferably a copolymer of 4-(meth)acryloylmorpholine and monomers or oligomers other than 4-(meth)acryloylmorpholine.

[0039] In the acrylic resin (b), the ratio of the amount of structural units derived from 4-(meth)acryloylmorpholine to the total amount of structural units (the total amount of all structural units possessed by the acrylic resin (b)) ([amount of structural units derived from 4-(meth)acryloylmorpholine in the acrylic resin (b) (parts by mass)] / [total amount of structural units in the acrylic resin (b) (parts by mass)] × 100) is 10% by mass or more, preferably 13% by mass or more, for example, it can be any range of 18% by mass or more and 23% by mass or more. By making the ratio above the lower limit value, the effect of inhibiting the peeling of the protective film from the wafer or chip becomes more effective.

[0040] In acrylic resin (b), there is no particular upper limit to the ratio of the amount of structural units derived from 4-(meth)acryloylmorpholine to the total amount of structural units. However, from the perspective of better balancing the properties of inhibiting the protective film from peeling off the wafer or chip, as well as other properties, the ratio is preferably 30% by mass or less.

[0041] In the acrylic resin (b), the ratio of the amount of structural units derived from 4-(meth)acryloylmorpholine to the total amount of structural units can be appropriately adjusted within a range set by any combination of the aforementioned lower and upper limits. For example, in one embodiment, the ratio is preferably 10–30% by mass, more preferably 13–30% by mass, and can be any range from 18–30% by mass to 23–30% by mass. However, these ranges are merely examples of the ratio.

[0042] When the acrylic resin (b) has only one of the structural units derived from 4-acryloylmorpholine and the structural units derived from 4-methacryloylmorpholine, in this specification, "the amount of structural units derived from 4-(meth)acryloylmorpholine" means either "the amount of structural units derived from 4-acryloylmorpholine" or "the amount of structural units derived from 4-methacryloylmorpholine". When the acrylic resin (b) has both structural units derived from 4-acryloylmorpholine and structural units derived from 4-methacryloylmorpholine, in this specification, "the amount of structural units derived from 4-(meth)acryloylmorpholine" refers to the sum of "the amount of structural units derived from 4-acryloylmorpholine" and "the amount of structural units derived from 4-methacryloylmorpholine".

[0043] At least a portion of the acrylic resin (b) may be cross-linked by a cross-linking agent, or it may not be cross-linked.

[0044] The acrylic resin (b) is preferably a copolymer of two or more monomers (in other words, having two or more structural units). It can be a copolymer of two or more acrylic monomers, or a copolymer of one or more acrylic monomers with one or more monomers other than acrylic monomers (non-acrylic monomers).

[0045] Examples of acrylic monomers constituting acrylic resin (b), other than 4-(meth)acryloylmorpholine, include alkyl (meth)acrylates without functional groups and cyclic skeletons, (meth)acrylates without functional groups but with cyclic skeletons, (meth)acrylates containing glycidyl groups, (meth)acrylates containing hydroxyl groups, (meth)acrylates containing substituted amino groups, (meth)acrylates containing carboxyl groups, and (meth)acrylates containing amino groups. Here, "substituted amino group" refers to a group having a structure in which one or two hydrogen atoms of an amino group are replaced by a group other than a hydrogen atom. Furthermore, "functional group" refers to a group, such as glycidyl group, hydroxyl group, substituted amino group, carboxyl group, or amino group, that can react with other groups (reactive functional groups).

[0046] Examples of alkyl (meth)acrylates that do not possess functional groups and a cyclic skeleton include, for example, 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, and (meth)acrylate Isononyl ester, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate (laurate methacrylate), tridecyl methacrylate, tetradecyl methacrylate (myristyl methacrylate), pentadecyl methacrylate, hexadecyl methacrylate (palmitoyl methacrylate), heptadecanyl methacrylate, octadecyl methacrylate (stearate methacrylate), etc., are alkyl esters in which the alkyl group has a chain structure with 1 to 18 carbon atoms.

[0047] Examples of (meth)acrylates that do not have functional groups but have a cyclic skeleton include isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, and other cycloalkyl (meth)acrylates. (Meth)benzyl acrylate and other (meth)acrylate aralkyl esters; (Meth)acrylate dicyclopentenyl ester and other (meth)acrylate cycloalkenyl esters; (Meth)acrylate dicyclopentenyloxyethyl ester, (meth)acrylate cyclopentenyloxyalkyl ester, etc.

[0048] Examples of glycidyl acrylates containing glycidyl groups include glycidyl acrylate. Examples of hydroxyl-containing (meth)acrylates include those having a structure in which one or more hydrogen atoms are replaced by hydroxyl groups in either alkyl (meth)acrylates lacking functional groups and cyclic skeletons or (meth)acrylates lacking functional groups but having cyclic skeletons. Preferred examples of hydroxyl-containing (meth)acrylates 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 substituted amino-containing (meth)acrylates include N-methylaminoethyl (meth)acrylate.

[0049] Examples of non-acrylic monomers constituting acrylic resin (b) include olefins such as ethylene and norbornene; vinyl acetate; styrene, etc.

[0050] As an acrylic resin (b) that is at least partially crosslinked by a crosslinking agent, examples include acrylic resins formed by reacting the functional groups of acrylic resin (b) with a crosslinking agent. The functional groups can be appropriately selected based on the type of crosslinking agent, and there are no particular limitations. For example, when the crosslinking agent is a polyisocyanate compound, hydroxyl, carboxyl, and amino groups can be listed as functional groups, among which hydroxyl groups with high reactivity with isocyanate groups are preferred. Furthermore, when the crosslinking agent is an epoxy compound, carboxyl and amino groups can be listed as functional groups, among which carboxyl groups with high reactivity with epoxy groups are preferred. From the perspective of preventing circuit corrosion on wafers or chips, functional groups other than carboxyl groups are preferred.

[0051] As an acrylic resin (b) having the aforementioned functional group, examples include acrylic resins obtained by polymerizing monomers having at least the aforementioned functional group. As an acrylic resin (b) having the aforementioned functional group, more specifically, examples include acrylic resins obtained by polymerizing one or more monomers selected from the group consisting of the glycidyl-containing (meth)acrylate, the hydroxyl-containing (meth)acrylate, the substituted amino-containing (meth)acrylate, the carboxyl-containing (meth)acrylate, the amino-containing (meth)acrylate, and monomers having a structure in which one or more hydrogen atoms in the non-acrylic monomer are replaced by the aforementioned functional group.

[0052] In the acrylic resin (b) having functional groups, the ratio (content) of the amount of structural units derived from monomers having functional groups relative to the total amount of structural units constituting the acrylic resin (b) is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. By keeping the ratio within the above range, the degree of crosslinking in the acrylic resin (b) is within a more preferred range.

[0053] Based on the fact that the film-forming properties of composition (IV) are improved, the weight-average molecular weight (Mw) of acrylic resin (b) is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000.

[0054] Unless otherwise specified in this specification, “weight-average molecular weight” refers to the converted value of polystyrene determined by gel permeation chromatography (GPC).

[0055] The acrylic resin (b) contained in the composition (IV) and the protective film formed therefrom can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0056] In composition (IV), the content of acrylic resin (b) relative to the total content of all components except the solvent (i.e., the ratio of the content of acrylic resin (b) in the protective film forming film to the total mass of the protective film forming film) is 8% by mass or more, preferably 10% by mass or more, for example, it can be any range of 12% by mass or more and 14% by mass or more. By making the ratio above the lower limit value, the effect of inhibiting the protective film from peeling off from the wafer or chip becomes more effective.

[0057] In composition (IV), there is no particular upper limit to the ratio of the content of acrylic resin (b) to the total content of all components except the solvent (i.e., the ratio of the content of acrylic resin (b) in the protective film forming film to the total mass of the protective film forming film). However, from the perspective of achieving a good balance between the properties of inhibiting the protective film from peeling off the wafer or chip and other properties, the ratio is preferably 25% by mass or less.

[0058] In composition (IV), the ratio of the content of acrylic resin (b) to the total content of all components except the solvent (i.e., the ratio of the content of acrylic resin (b) in the protective film forming film to the total mass of the protective film forming film) can be appropriately adjusted within a range set by any combination of the aforementioned lower and upper limits. For example, in one embodiment, the ratio is preferably 8 to 25% by mass, more preferably 10 to 25% by mass, and can be any range from 12 to 25% by mass and 14 to 25% by mass. However, these ranges are merely examples of the ratio.

[0059] [Energy-based solidification component (a)] The energy-curable component (a) is a component that is cured by irradiation with energy rays. It is also a component used to impart film-forming properties, flexibility, etc., to the protective film, and to form a hard protective film after curing. By further containing the energy-curable component (a), the protective film forms a protective film with good properties. In the protective film forming film, the energy-curable component (a) is preferably uncured, more preferably adhesive, and even more preferably uncured and adhesive.

[0060] Examples of energy-curable components (a) include polymers (a1) with a weight-average molecular weight of 80,000 to 2,000,000 having energy-curable groups, and compounds (a2) with a molecular weight of 100 to 80,000 having energy-curable groups. At least a portion of the polymer (a1) may be cross-linked by a cross-linking agent, or it may not be cross-linked.

[0061] (Polymers with a weight-average molecular weight of 80,000 to 2,000,000 that have energy-ray curable groups (a1)) As a polymer (a1) with a weight average molecular weight of 80,000 to 2,000,000 having energy-curable groups, an example is an acrylic resin (a1-1) formed by reacting an acrylic polymer (a11) with an energy-curable compound (a12). The acrylic polymer (a11) has functional groups that can react with groups of other compounds, and the energy-curable compound (a12) has groups that react with the functional groups and energy-curable groups such as energy-curable double bonds.

[0062] Functional groups capable of reacting with groups found in other compounds include, for example, hydroxyl, carboxyl, amino, substituted amino (a group having a structure in which one or two hydrogen atoms of an amino group are replaced by a group other than hydrogen atoms), epoxy, etc. Among these, from the perspective of preventing circuit corrosion of wafers or chips, the functional group is preferably a group other than a carboxyl group. The functional group is preferably a hydroxyl group.

[0063] • Acrylic polymers with functional groups (a11) As an example of the acrylic polymer (a11) having the functional group, a polymer can be formed by copolymerizing an acrylic monomer having the functional group with an acrylic monomer not having the functional group, or a polymer formed by further copolymerizing monomers other than acrylic monomers (non-acrylic monomers) in addition to these monomers. Furthermore, the acrylic polymer (a11) can be a random copolymer or a block copolymer, and the polymerization method can also be a known method.

[0064] Examples of acrylic monomers having the aforementioned functional groups include hydroxyl-containing monomers, carboxyl-containing monomers, amino-containing monomers, substituted amino-containing monomers, and epoxy-containing monomers.

[0065] Examples of hydroxyl-containing monomers include hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, and other hydroxyalkyl methacrylates; and non-methacrylic unsaturated alcohols (unsaturated alcohols without a methacryloyl skeleton) such as vinyl alcohol and allyl alcohol.

[0066] Examples of carboxyl-containing monomers include, for example, (meth)acrylic acid, crotonic acid, and other olefinically unsaturated monocarboxylic acids (monocarboxylic acids having olefinically unsaturated bonds); fumaric acid, itaconic acid, maleic acid, citraconic acid, and other olefinically unsaturated dicarboxylic acids (dicarboxylic acids having olefinically unsaturated bonds); anhydrides of the aforementioned olefinically unsaturated dicarboxylic acids; and (meth)acrylic acid carboxylalkyl esters such as 2-carboxyethyl methacrylate.

[0067] The acrylic monomer having the aforementioned functional group is preferably a hydroxyl-containing monomer.

[0068] The acrylic monomers having the functional groups constituting the acrylic polymer (a11) can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0069] Examples of acrylic monomers that do not possess the aforementioned functional groups include, for example, 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, and so on. Alkyl esters, such as decyl methacrylate, undecyl methacrylate, dodecyl methacrylate (laurate methacrylate), tridecyl methacrylate, tetradecyl methacrylate (myristyl methacrylate), pentadecyl methacrylate, hexadecyl methacrylate (palmitoyl methacrylate), heptadecanyl methacrylate, and octadecyl methacrylate (stearic acid ester), are chain alkyl esters in which the alkyl group has a carbon atom number of 1 to 18.

[0070] In addition, examples of acrylic monomers that do not have the aforementioned functional groups include methoxymethyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, ethoxyethyl methacrylate, and other (meth)acrylates containing alkoxyalkyl groups; (meth)acrylates containing aromatic groups, including aryl methacrylates such as phenyl methacrylate; non-crosslinked (meth)acrylamide and its derivatives; and non-crosslinked (meth)acrylates containing tertiary amino groups, such as N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminopropyl methacrylate.

[0071] In this specification, when a particular compound has a structure in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms, the compound having the structure formed by such substitution is referred to as a "derivative" of the particular compound. In this specification, "group" includes not only groups of atoms bonded together, but also a single atom.

[0072] The acrylic monomers that do not have the functional groups constituting the acrylic polymer (a11) can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0073] Examples of non-acrylic acid monomers include, for example, olefins such as ethylene and norbornene; vinyl acetate; and styrene. The non-acrylic monomers constituting the acrylic polymer (a11) may be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0074] In the acrylic polymer (a11), the ratio (content) of the structural units derived from the acrylic monomer having the functional group to the total amount of 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 keeping the ratio within the above range, the content of energy-curable groups in the acrylic resin (a1-1) obtained by copolymerizing the acrylic polymer (a11) with the energy-curable compound (a12) can be adjusted to a preferred range to control the degree of curing of the protective film.

[0075] The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0076] The content of acrylic resin (a1-1) in the protective film forming film relative to the total mass of the protective film forming film is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass.

[0077] • Energy-curing compounds (a12) The energy-curable compound (a12) preferably has one or more groups selected from the group consisting of isocyanate groups, epoxy groups, and carboxyl groups as functional groups capable of reacting with the functional groups of the acrylic polymer (a11), and more preferably has an isocyanate group as the functional group. For example, when the energy-curable compound (a12) has an isocyanate group as the functional group, the isocyanate group readily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

[0078] The number of energy-curing groups in a molecule of the energy-curing compound (a12) is not particularly limited, and can be appropriately selected, for example, taking into account the physical properties such as shrinkage required for the target protective film. For example, the energy-curing compound (a12) preferably has 1 to 5 energy-curing groups in one molecule, more preferably 1 to 3 energy-curing groups.

[0079] Examples of energy-curable compounds (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. Acryloyl monoisocyanate compounds are obtained by reacting diisocyanate compounds or polyisocyanate compounds with hydroxyethyl (meth)acrylate. Acryloyl monoisocyanate compounds, etc., are obtained by reacting diisocyanate compounds or polyisocyanate compounds with polyol compounds and hydroxyethyl (meth)acrylate. The energy-curable compound (a12) is preferably 2-methacryloyloxyethyl isocyanate.

[0080] The energy-curable compound (a12) constituting the acrylic resin (a1-1) may be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0081] In the acrylic resin (a1-1), the ratio of the content of the energy-curable groups from the energy-curable compound (a12) to the content of the functional groups from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly preferably 50 to 100 mol%. By keeping the content ratio within the above range, the adhesive strength of the cured protective film is further increased. Furthermore, when the energy-curable compound (a12) is a monofunctional compound (having one of the aforementioned groups in one molecule), the upper limit of the content ratio is 100 mol%, but when the energy-curable compound (a12) is a polyfunctional compound (having two or more of the aforementioned groups in one molecule), the upper limit of the content ratio may sometimes exceed 100 mol%.

[0082] The weight-average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000. The "weight-average molecular weight" is as described above.

[0083] The polymer (a1) contained in the composition (IV) and the protective film can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0084] (Compounds with energy-ray-curing functional groups and molecular weights ranging from 100 to 80,000 (a2)) The energy-curing group in the compound (a2) having an energy-curing group and a molecular weight of 100 to 80,000 can be a group containing an energy-curing double bond, and preferred groups include (meth)acryloyl, vinyl, etc.

[0085] As long as the above conditions are met, the compound (a2) is not particularly limited, and examples include low molecular weight compounds with energy-curable groups, epoxy resins with energy-curable groups, phenolic resins with energy-curable groups, etc.

[0086] As a low molecular weight compound having an energy-curable group in compound (a2), examples include multifunctional monomers or oligomers, and preferably acrylate compounds having a (meth)acryloyl group.

[0087] Examples of the acrylate compounds include, for example, multifunctional monomers or oligomers, with multifunctional acrylate compounds having two or more (meth)acryloyl groups in one molecule being preferred. Examples of such multifunctional acrylate compounds include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxyethyl bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethyl bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloyloxypolypropoxy)phenyl]propane, tricyclodecanediethanol di(meth)acrylate (also known as tricyclodecanedihydroxymethyl di(meth)acrylate), and 1,10-decanediol dimethacrylate. (Meth)acrylates, 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, polybutylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloyloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane and other difunctional (meth)acrylates (meth)acrylates having two (meth)acryloyl groups in one molecule); Tris(2-(meth)acryloyloxyethyl)isocyanurate, ε-caprolactone-modified tri-(2-(meth)acryloyloxyethyl)isocyanurate, glyceryl ethoxylate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate ethoxylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other multifunctional (meth)acrylates ((meth)acrylates having three or more (meth)acryloyl groups in one molecule); Multifunctional urethane (meth)acrylate oligomers and other multifunctional (meth)acrylate oligomers ((meth)acrylate oligomers having two or more (meth)acryloyl groups in one molecule), etc.

[0088] As the epoxy resin having energy-curable groups or the phenolic resin having energy-curable groups in the compound (a2), compounds such as those described in paragraph 0043 of Japanese Patent Application Publication No. 2013-194102 may be used. Although the above-mentioned resins also belong to the category of resins constituting the thermosetting components described later, they are regarded as the compound (a2) in the composition (IV).

[0089] The weight-average molecular weight of the compound (a2) is preferably 100 to 30,000, more preferably 300 to 10,000.

[0090] The compound (a2) contained in the composition (IV) and the protective film forming film can be only one or more. When there are more than two, their combination and ratio can be arbitrarily selected.

[0091] The protective film forming film preferably contains the compound (a2) as an energy-curable component (a), more preferably it contains a polyfunctional acrylate compound having two or more (meth)acryloyl groups in one molecule, and even more preferably it contains a polyfunctional urethane (meth)acrylate oligomer. The protective film forming film containing the above-mentioned energy-curable component (a), when cured by irradiation with energy rays, has good protective properties and flexibility, exhibiting particularly excellent characteristics.

[0092] When the composition (IV) and the protective film forming film contain an energy-curable component (a), the content of the energy-curable component (a) in the composition (IV) and the protective film forming film is preferably 100 to 310 parts by mass relative to the content of acrylic resin (b) per 100 parts by mass, more preferably 130 to 280 parts by mass, for example, 130 to 200 parts by mass, or 210 to 280 parts by mass.

[0093] In composition (IV), the ratio of the total content of the energy-curable component (a) and the acrylic resin (b) to the total content of all components except the solvent (i.e., the ratio of the total content of the energy-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, for example, it can be any range from 20 to 50% by mass and 30 to 45% by mass. By keeping the ratio within the above range, the effect obtained by using the energy-curable component (a) and the acrylic resin (b) becomes greater.

[0094] [Other ingredients] Without impairing the effects of the present invention, the composition (IV) and the protective film forming film may also contain other components that are neither acrylic resin (b) nor energy-curable component (a). Other components may include, for example, photopolymerization initiators (c), inorganic fillers (d), coupling agents (e), crosslinking agents (f), colorants (g), thermosetting components (h), general additives (z), and polymers (b0) that do not belong to acrylic resins (b) and do not have energy-curable groups (b0) (in this specification, they are sometimes referred to as "other polymers (b0) that do not have energy-curable groups" or "polymers (b0)").

[0095] ((Photopolymerization initiator(c)) When the composition (IV) and the protective film form contain a photopolymerization initiator (c), the polymerization (curing) reaction of the energy-curable component (a) can be effectively carried out.

[0096] Examples of photopolymerization initiators include benzoin compounds such as 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 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one, and 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone; and phenyl bis(2,4,6-trimethylphenyl)-phenylpropane-1-one. Acylphosphine oxides such as methylbenzoyl(phosphine)oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohols such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; diacetic compounds such as diaceticotitanium; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzil; dibenzo-p-ethyl; 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. In addition, photosensitizers such as amines can also be listed as photopolymerization initiators.

[0097] The photopolymerization initiator (c) contained in the composition (IV) and the protective film can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0098] When using a photopolymerization initiator (c), in the composition (IV), the content of the photopolymerization initiator (c) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the energy-curable component (a), more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass.

[0099] (Inorganic filler material (d)) When the composition (IV) and the protective film forming film contain inorganic filler (d), by adjusting the amount of inorganic filler (d) in the composition (IV) and the protective film forming film, the coefficient of thermal expansion of the cured product of the protective film forming film (e.g., the protective film) can be more easily adjusted. For example, by optimizing the coefficient of thermal expansion of the protective film for the object to which the protective film is formed, the reliability of the encapsulation obtained using the protective film forming film is further improved. Furthermore, by using a protective film forming film containing inorganic filler (d), the moisture absorption rate of the cured product of the protective film forming film (e.g., the protective film) can be reduced and the heat dissipation can be improved.

[0100] Examples of inorganic filler materials (d) include powders of inorganic materials such as silicon dioxide, alumina, talc, calcium carbonate, titanium dioxide, red iron oxide, silicon carbide, and boron nitride; beads formed by spherizing these inorganic fillers; surface modifiers of these inorganic fillers; single-crystal fibers of these inorganic fillers; and glass fibers. Among them, the inorganic filler material (d) is preferably silicon dioxide or aluminum oxide.

[0101] The inorganic filler material (d) contained in the composition (IV) and the protective film can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0102] In composition (IV), the ratio of the content of inorganic filler (d) to the total content of all components except the solvent (i.e., the ratio of the content of inorganic filler (d) in the protective film forming film to the total mass of the protective film forming film) is preferably 35 to 75% by mass, for example, it can be any range from 45 to 70% by mass and 50 to 65% by mass. By keeping the ratio within the above range, the properties of the protective film forming film are not impaired, and the effect obtained by using inorganic filler (d) is enhanced.

[0103] (Coupled agent(e)) When the composition (IV) and the protective film forming film contain a coupling agent (e) having functional groups capable of reacting with inorganic or organic compounds, the adhesion and bonding strength of the protective film forming film to the adhered object are increased. Furthermore, the heat resistance and water resistance of the cured protective film forming film (e.g., the protective film) are not impaired.

[0104] The coupling agent (e) is preferably a compound having a functional group that can react with the functional groups of the acrylic resin (b), the energy-curable component (a), etc., and more preferably a silane coupling agent. Preferred silane coupling agents include, for example, 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropylmethyldiethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 3-glycidyl etheroxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-(2-aminoethylamino)propyltrimethoxysilane. Oxysilanes, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinepropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, etc.

[0105] The coupling agent (e) contained in the composition (IV) and the protective film can be only one or more. When there are more than two, their combination and ratio can be arbitrarily selected.

[0106] When using coupling agent (e), the content of coupling agent (e) in the composition (IV) and the protective film forming film is preferably 0.03 to 20 parts by mass relative to the total content of the energy-curable component (a) and acrylic resin (b) of 100 parts by mass. By setting the content of coupling agent (e) to the lower limit or above, the effects of using coupling agent (e), such as improving the dispersibility of inorganic filler material (d) in the resin or improving the adhesion between the protective film forming film and the adherend, can be obtained more significantly. By setting the content of coupling agent (e) to the upper limit or below, the generation of outgassing can be further suppressed.

[0107] (Cross-linking agent(f)) When an acrylic resin (b) is used, having functional groups such as vinyl, (meth)acryloyl, amino, hydroxyl, carboxyl, and isocyanate groups that can bond with other compounds, the composition (IV) and the protective film forming film may contain a crosslinking agent (f). The crosslinking agent (f) is a component used to crosslink the functional groups in the acrylic resin (b) with other compounds, thereby adjusting the initial adhesiveness and cohesiveness of the protective film forming film.

[0108] Examples of crosslinking agents (f) include organic polyisocyanate compounds, organic polyimide compounds, metal chelate crosslinking agents (crosslinking agents with metal chelate structures), and aziridine crosslinking agents (crosslinking agents with aziridine groups).

[0109] Examples of such organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter, these compounds are sometimes collectively referred to as "aromatic polyisocyanate compounds, etc."); trimers, isocyanurates, and adducts of such aromatic polyisocyanate compounds, etc.; and terminal isocyanate carbamate prepolymers obtained by reacting such aromatic polyisocyanate compounds, etc., with polyol compounds. The term "adduct" refers to the reaction product of such aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, or alicyclic polyisocyanate compounds with low-molecular-weight compounds containing active hydrogen, such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. Examples of such adducts include the phenylene diisocyanate adduct of trimethylolpropane, as described later. Furthermore, "terminal isocyanate carbamate prepolymers" refers to prepolymers having carbamate bonds and simultaneously having isocyanate groups at the terminal end of the molecule.

[0110] More specifically, examples of such organic polyisocyanate compounds include, for instance, compounds obtained by adding all or part of the hydroxyl groups of polyols such as 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-phenylenedimethylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylolpropane; and lysine diisocyanate, etc., to any one or more of the hydroxyl groups of toluene diisocyanate, hexamethylene diisocyanate, and phenylenedimethylene diisocyanate.

[0111] Examples of such organic polyimide compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridinylcarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, and N,N'-toluene-2,4-bis(1-aziridinylcarboxamide)triethylene melamine.

[0112] When an organic polyisocyanate compound is used as a crosslinking agent (f), a hydroxyl-containing polymer is preferably used as the acrylic resin (b). When the crosslinking agent (f) has isocyanate groups and the acrylic resin (b) has hydroxyl groups, a crosslinked structure can be easily introduced into the protective film forming film through the reaction of the crosslinking agent (f) and the acrylic resin (b).

[0113] The crosslinking agent (f) contained in the composition (IV) and the protective film can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0114] When crosslinking agent (f) is used, in composition (IV), the content of crosslinking agent (f) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of acrylic resin (b). By setting the content of crosslinking agent (f) to the lower limit or above, the effect of using crosslinking agent (f) can be obtained more significantly. By setting the content of crosslinking agent (f) to the upper limit or below, the excessive use of crosslinking agent (f) can be suppressed.

[0115] (Coloring agent (g)) When the composition (IV) and the protective film forming film contain a colorant (g), the transmittance of the protective film forming film can be adjusted by regulating its content. Furthermore, by adjusting the transmittance in this way, for example, the visibility of the printed text when laser printing is performed on the protective film forming film or the protective film can be adjusted. In addition, the design flexibility of the protective film can be improved, and grinding marks on the back side of the wafer are less likely to be detected.

[0116] As coloring agents (g), examples include known coloring agents such as inorganic pigments, organic pigments, and organic dyes.

[0117] Examples of organic pigments and dyes include, for example, aminium pigments, anthocyanin pigments, croconium pigments, squarylium pigments, azulenium pigments, polymethystylene pigments, naphthoquinone pigments, pyranium pigments, phthalocyanine pigments, naphthocyanin pigments, naphtholactam pigments, azo pigments, and condensed doublet pigments. Nitrogen-based pigments, indigo-based pigments, perinone-based pigments, perylene-based pigments, dioxazine-based pigments, quinacridone-based pigments, isoindolineone-based pigments, quinolineone-based pigments, pyrrole-based pigments, thioindigo-based pigments, metal complex pigments (metal complex salt dyes), dithiol metal complex pigments, indolephenol-based pigments, triarylmethane-based pigments, anthraquinone-based pigments, naphthol-based pigments, methylimino-based pigments, benzimidazole-based pigments, pinantrone-based pigments, and threne-based pigments, etc.

[0118] Examples of 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, and ATO (antimony tin oxide) pigments.

[0119] The colorant (g) contained in the composition (IV) and the protective film can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0120] When using a colorant (g), the content of the colorant (g) in the composition (IV) and the protective film forming film can be appropriately selected according to the purpose. For example, as described above, when improving the visibility of the printed text on the protective film forming film or the design of the protective film, or making it less likely to detect grinding marks on the back side of the wafer, the ratio of the content of the colorant (g) in the composition (IV) to the total content of all components except the solvent (i.e., the ratio of the content of the colorant (g) in the protective film forming film to the total mass of the protective film forming film) is preferably 0.05 to 12% by mass, more preferably 0.05 to 9% by mass, and particularly preferably 0.1 to 7% by mass. By setting the ratio to the lower limit or above, the effect of using the colorant (g) can be obtained more significantly. By setting the ratio to the upper limit or below, the excessive use of the colorant (g) can be suppressed.

[0121] (Thermosetting component (h)) When the composition (IV) and the protective film forming film contain an energy-curable component (a) and a thermosetting component (h), the adhesive force of the protective film forming film to the adhered object increases when the protective film forming film is heated, and the strength of the cured product of the protective film forming film (e.g., the protective film) also increases.

[0122] Examples of thermosetting components (h) include epoxy thermosetting resins, polyimide resins, and unsaturated polyester resins, with epoxy thermosetting resins being preferred.

[0123] The epoxy thermosetting resin is composed of epoxy resin (h1) and thermosetting agent (h2). The epoxy thermosetting resin contained in the composition (IV) and the protective film can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0124] ·Epoxy resin (h1) As for epoxy resin (h1), well-known epoxy resins can be listed, such as multifunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrides, o-cresol phenolic varnish epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and other epoxy compounds with more than one function.

[0125] As the epoxy resin (h1), an epoxy resin having unsaturated hydrocarbon groups can be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin with unsaturated hydrocarbon groups, the reliability of the chip with a protective film obtained using a composite sheet for forming a protective film is increased.

[0126] As an epoxy resin having unsaturated hydrocarbon groups, for example, a compound formed by converting some of the epoxy groups of a multifunctional epoxy resin into groups having unsaturated hydrocarbon groups. This compound can be obtained, for example, by reacting (meth)acrylic acid or a derivative thereof with an epoxy group via an addition reaction. Furthermore, examples of epoxy resins containing unsaturated hydrocarbon groups include compounds formed by directly bonding unsaturated hydrocarbon groups to aromatic rings that constitute the epoxy resin. Unsaturated hydrocarbon groups are unsaturated groups that can polymerize. Specific examples include methine (vinyl), 2-propenyl (allyl), (meth)acryloyl, (meth)acrylamido, etc., with acryloyl being preferred.

[0127] The number average molecular weight of epoxy resin (h1) is not particularly limited, but from the perspective of the curability of the protective film, as well as the strength and heat resistance of the protective film, it is preferably 300 to 30000, more preferably 300 to 10000, and particularly preferably 300 to 3000. The epoxy equivalent of the epoxy resin (h1) is preferably 100 to 1000 g / eq, more preferably 150 to 950 g / eq.

[0128] The epoxy resin (h1) contained in the composition (IV) and the protective film can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0129] • Thermosetting agent (h2) The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1). As a thermosetting agent (h2), examples include compounds having two or more functional groups in one molecule that can react with epoxy groups. Examples of such functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and groups formed by anhydride modification of acid groups; phenolic hydroxyl groups, amino groups, or groups formed by anhydride modification of acid groups are preferred, and phenolic hydroxyl groups or amino groups are more preferred.

[0130] Phenolic curing agents with phenolic hydroxyl groups, such as polyfunctional phenolic resins, biphenyl, phenolic varnish-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins, are examples of thermosetting agents (h2). Amine curing agents containing amino groups, such as dicyandiamide, can be used as thermosetting agents (h2).

[0131] Thermosetting agents (h2) can have unsaturated hydrocarbon groups. Examples of thermosetting agents (h2) with unsaturated hydrocarbon groups include compounds formed by replacing some of the hydroxyl groups of phenolic resin with groups having unsaturated hydrocarbon groups, and compounds formed by directly bonding groups having unsaturated hydrocarbon groups to the aromatic ring of phenolic resin. The unsaturated hydrocarbon group in the thermosetting agent (h2) can be an example of a group that is the same as the unsaturated hydrocarbon group in the epoxy resin having the unsaturated hydrocarbon group described above.

[0132] When using a phenolic curing agent as a thermosetting agent (h2), a thermosetting agent (h2) with a high softening point or glass transition temperature is preferred from the perspective of improving the peelability of the protective film when it is peeled off from the support sheet.

[0133] In the thermosetting agent (h2), for example, the number average molecular weight of the resin components such as multifunctional phenolic resin, phenolic varnish-type phenolic resin, dicyclopentadiene-type phenolic resin, and aralkyl-type phenolic resin is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000. In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenyl hydroquinone and dicyandiamide is not particularly limited, but is preferably 60 to 500.

[0134] The thermosetting agent (h2) contained in the composition (IV) and the protective film can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0135] When using a thermosetting component (h), the content of the thermosetting agent (h2) in the composition (IV) and the protective film forming film is preferably 0.1 to 100 parts by mass relative to 100 parts by mass of epoxy resin (h1). By setting the content of the thermosetting agent (h2) to the lower limit or above, it is easier to cure the protective film forming film. By setting the content of the thermosetting agent (h2) to the upper limit or below, the moisture absorption rate of the protective film forming film is reduced, and the reliability of the package obtained using the chip with the protective film is further increased.

[0136] When using the thermosetting component (h), in the composition (IV) and the protective film forming film, the content of the thermosetting component (h) (e.g., the total content of epoxy resin (h1) and thermosetting agent (h2)) is preferably 5 to 120 parts by mass relative to 100 parts by mass of acrylic resin (b). By keeping the content of the thermosetting component (h) within the above range, for example, the adhesion between the cured protective film forming film and the support sheet is suppressed, and the peelability of the support sheet is increased.

[0137] (General Additives (z)) The general additive (z) can be any known additive and can be selected arbitrarily according to the purpose without particular limitation. Preferred general additives (z) include, for example, plasticizers, antistatic agents, antioxidants, impurities absorbers, and ultraviolet absorbers.

[0138] The general additives (z) contained in the composition (IV) and the protective film forming film can be only one or more. When there are more than two, their combination and ratio can be arbitrarily selected.

[0139] When using a general additive (z), there is no particular limitation on the content of the composition (IV) and the general additive (z) forming the protective film; it can be selected appropriately according to the purpose. For example, when the general additive (z) is a UV absorber, the ratio of the content of the general additive (z) (UV absorber) in the composition (IV) to the total content of all components except the solvent (i.e., the ratio of the content of the general additive (z) (UV 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 above the lower limit, the effect of using the general additive (z) can be obtained more significantly. By setting the ratio below the upper limit, the excessive use of the general additive (z) can be suppressed.

[0140] (Other polymers that do not have energy-curing groups (b0)) Other polymers (b0) that do not have energy-curable groups impart film-forming properties to the protective film. The polymer (b0) is not particularly limited as long as it is not an acrylic resin (b). At least a portion of the polymer (b0) may be cross-linked by a cross-linking agent, or it may not be cross-linked.

[0141] Examples of the polymer (b0) include acrylic resins in which the ratio of the amount of 4-(meth)acryloylmorpholine-derived structural units in the acrylic resin to the total amount of structural units ([amount of 4-(meth)acryloylmorpholine-derived structural units in the acrylic resin (parts by mass)] / [total amount of structural units in the acrylic resin (parts by mass)]×100) is 0% by mass or more and less than 10% by mass (sometimes referred to as "other acrylic resins" in this specification); polymers other than acrylic resins that do not have energy-curable groups.

[0142] As other acrylic resins mentioned above, examples include acrylic resins that are the same as acrylic resin (b), except that the proportion of the structural unit derived from 4-(meth)acryloylmorpholine is 0% or more by mass and less than 10% by mass, rather than 10% or more by mass.

[0143] Examples of polymers other than acrylic resins that do not have energy-curable groups include urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.

[0144] From the point that the film-forming properties of composition (IV) are improved, the weight-average molecular weight (Mw) of polymers other than acrylic resins that do not have energy-curable groups is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000.

[0145] The polymer (b0) contained in the composition (IV) and the protective film can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0146] In the composition (IV) and the protective film forming film, the content of 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 parts by mass, that is, it is particularly preferred that the composition (IV) and the protective film forming film do not contain polymer (b0). By keeping the content of polymer (b0) below the upper limit value, the effect of inhibiting the protective film from peeling off from the wafer or chip becomes more significant.

[0147] [solvent] Composition (IV) preferably further contains a solvent. Composition (IV) containing a solvent has good operability. The solvent is not particularly limited, but preferred solvents include, for example, 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; and amides (compounds with amide bonds) such as dimethylformamide and N-methylpyrrolidone. The composition (IV) may contain only one solvent or two or more solvents. When there are two or more solvents, their combination and ratio can be arbitrarily selected.

[0148] From the perspective that the components contained in composition (IV) can be mixed more uniformly, methyl ethyl ketone and the like can be listed as more preferred examples among the solvents contained in composition (IV).

[0149] The solvent content of composition (IV) is not particularly limited; for example, it can be appropriately selected according to the types of components other than the solvent.

[0150] <<Preparation Method of Composition for Protective Film Formation>> Composition (IV) is a composition for forming a protective film that can be cured by energy rays, which can be obtained by incorporating the components used to constitute the composition. There is no particular restriction on the order of addition when mixing the ingredients, and two or more ingredients can be added at the same time. There are no particular limitations on the method of mixing the components during blending; any appropriate method may be selected from the following known methods: mixing by rotating a stir bar or stirring blade; mixing by using a mixer; mixing by applying ultrasound, etc. As long as the individual blended components do not deteriorate, there are no particular limitations on the temperature and time when adding and mixing the components; they can be adjusted appropriately. However, the preferred temperature is 15℃ to 30℃.

[0151] Figure 1 A cross-sectional view is shown schematically as an example of the protective film forming film of this embodiment. Additionally, for ease of understanding of the features of the invention, important portions of the figures used in the following description are sometimes enlarged, and the dimensions and proportions of the constituent elements are not necessarily the same as in reality.

[0152] The protective film forming film 13 shown herein has a first release film 151 on one side (sometimes referred to as the "first side" in this specification) 13a, and a second release film 152 on the other side (sometimes referred to as the "second side" in this specification) 13b opposite to the first side 13a. The aforementioned protective film forming film 13 is, for example, suitable for preservation in roll form.

[0153] The protective film forming film 13 has the above-mentioned characteristics. The protective film forming film 13 can be formed using the above-described protective film forming composition.

[0154] Both the first release membrane 151 and the second release membrane 152 can be known release membranes. The first peeling film 151 and the second peeling film 152 can be connected to each other or different from each other. For example, the peeling forces required to peel from the protective film forming film 132 are different from each other.

[0155] for Figure 1 The protective film forming film 13 shown has an exposed surface created by removing either the first release film 151 or the second release film 152, which is the attachment surface to the back side of the wafer (not shown). Furthermore, the exposed surface created by removing the remaining one of the first release film 151 and the second release film 152 is the attachment surface to the support sheet or dicing sheet, which will be described later.

[0156] exist Figure 1 The example shown is that a release film is provided on both sides (first side 13a, second side 13b) of the protective film forming film 13, but the release film may also be provided on only one side of the protective film forming film 13, that is, only on the first side 13a or only on the second side 13b.

[0157] As an example of a preferred protective film forming membrane according to this embodiment, the following protective film forming membranes can be listed: One type is a protective film formed by energy-ray curing. The protective film forming film contains acrylic resin (b) without energy-curable groups, energy-curable component (a), and inorganic filler material (d). The acrylic resin (b) has structural units derived from 4-(meth)acryloylmorpholine. In the acrylic resin (b), the proportion of the structural unit derived from 4-(meth)acryloylmorpholine relative to the total amount of structural units is in any range of 10% by mass or more, 13% by mass or more, 18% by mass or more, and 23% by mass or more. In the protective film forming membrane, the content of the acrylic resin (b) relative to the total mass of the protective film forming membrane is within any range of 8% by mass or more, 10% by mass or more, 12% by mass or more, and 14% by mass or more. In the protective film forming film, relative to 100 parts by mass of the acrylic resin (b), the content of the energy-curable component (a) is in any range of 100-310 parts by mass, 130-280 parts by mass, 130-200 parts by mass, and 210-280 parts by mass. The content of the inorganic filler material (d) in the protective film forming membrane, relative to the total mass of the protective film forming membrane, is in any range of 35-75% by mass, 45-70% by mass, and 50-65% by mass. In the protective film forming film, the total content of the acrylic resin (b), the energy-curable component (a), and the inorganic filler (d) is no more than 100% by mass relative to the total mass of the protective film forming film.

[0158] As another example of a preferred protective film forming membrane according to this embodiment, the following protective film forming membranes can be listed: A protective film formed by energy radiation curing. The protective film forming film contains an acrylic resin (b) without energy-curable groups, an energy-curable component (a), and an inorganic filler (d). The acrylic resin (b) has structural units derived from 4-(meth)acryloylmorpholine. In the acrylic resin (b), the proportion of the structural unit derived from 4-(meth)acryloylmorpholine relative to the total amount of structural units is in any range of 10% by mass or more, 13% by mass or more, 18% by mass or more, and 23% by mass or more. In the protective film forming membrane, the content of the acrylic resin (b) relative to the total mass of the protective film forming membrane is within any range of 8% by mass or more, 10% by mass or more, 12% by mass or more, and 14% by mass or more. In the protective film forming film, relative to 100 parts by mass of the acrylic resin (b), the content of the energy-curable component (a) is in any range of 100-310 parts by mass, 130-280 parts by mass, 130-200 parts by mass, and 210-280 parts by mass. The content of the inorganic filler material (d) in the protective film forming membrane, relative to the total mass of the protective film forming membrane, is in any range of 35-75% by mass, 45-70% by mass, and 50-65% by mass. In the protective film forming film, the total content of the acrylic resin (b), the energy-curable component (a), and the inorganic filler (d) relative to the total mass of the protective film forming film is not greater than 100% by mass. A test piece of a 200 μm thick protective film forming membrane, consisting of multiple protective film layers, was held at two points with a 20 mm gap. Under testing conditions of a stretching mode at 11 Hz, a heating rate of 3 °C / min, and a temperature range of -10 °C to 140 °C, the storage modulus E' of the test piece of the protective film forming membrane was measured between these two points. The storage modulus E' of the test piece of the protective film forming membrane at 70 °C was then measured. 70 Any range of 30MPa or below, 10MPa or below, and 5MPa or below At an illuminance of 200 mW / cm² 2 The light intensity is 300 mJ / cm² 2 Under certain conditions, a multi-layer protective film with a thickness of 50 μm was irradiated twice from each side with ultraviolet light at a wavelength of 365 nm, thereby curing the protective film and producing a protective film test piece. The test piece was held at two points with a 20 mm gap between them. Under the conditions of a stretching mode at a frequency of 11 Hz, a heating rate of 3 °C / min, and a temperature range of 0 °C to 300 °C, the storage modulus E' of the protective film test piece was measured between these two points. The storage modulus E' of the protective film test piece at 130 °C was then measured. 130 It is any range of 5MPa or above, 8MPa or above, and 10MPa or above.

[0159] The protective film forming film of this embodiment can be attached to the back side of the wafer without being used simultaneously with the support sheet described later. In this case, a release film can be provided on the side of the protective film forming film opposite to the attachment surface of the wafer, and the release film can be removed at an appropriate time.

[0160] On the other hand, by using the protective film forming film of this embodiment and the support sheet described later at the same time, a composite sheet for forming a protective film can be constructed that can simultaneously form and cut the protective film. The following describes the composite sheet used to form this protective film.

[0161] ◇ Composite sheet for protective film formation A protective film forming composite sheet according to one embodiment of the present invention includes a support sheet and a protective film forming film disposed on one surface of the support sheet, wherein the protective film forming film is the protective film forming film of the above embodiment of the present invention. The protective film forming composite sheet of this embodiment, by having the protective film forming film, can suppress the peeling of the protective film from the wafer or chip during the formation of the protective film.

[0162] In this specification, as long as the laminated structure between the support sheet and the cured protective film can be maintained, the laminated structure will still be referred to as a "composite sheet for forming a protective film" even after the protective film has been cured.

[0163] The following is a detailed description of each layer constituting the composite sheet for forming the protective film.

[0164] ◎Supporting plate The support sheet can be composed of one layer (single layer) or multiple layers (two or more layers). When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers can be the same or different from each other. As long as the effect of the present invention is not impaired, there is no particular limitation on the combination of these multiple layers.

[0165] The support sheet is preferably transparent, but it can also be colored depending on the purpose. In this embodiment where the protective film forming film has energy-curing properties, the support sheet is preferably transmissible to energy rays.

[0166] Examples of support sheets include those having a substrate and an adhesive layer disposed on one side of the substrate; and support sheets consisting only of a substrate. When the support sheet has an adhesive layer, in a composite sheet for forming a protective film, the adhesive layer is disposed between the substrate and the protective film forming film.

[0167] When a support sheet with a substrate and an adhesive layer is used, the adhesion and peelability between the support sheet and the protective film forming film can be easily adjusted in the composite sheet for forming the protective film. When a support sheet consisting only of a substrate is used, a composite sheet for forming a protective film can be manufactured at low cost.

[0168] Hereinafter, examples of composite sheets for forming protective films according to the type of support sheet will be described with reference to the accompanying drawings.

[0169] Figure 2 A cross-sectional view is shown to illustrate an example of the composite sheet for forming the protective film according to this embodiment. In addition, Figure 2 In subsequent figures, for constituent elements that are the same as those shown in the previously described figures, the same symbols are used as in the previously described figures, and their detailed descriptions are omitted.

[0170] The protective film forming composite sheet 101 shown herein is constructed by having a support sheet 10 and a protective film forming film 13 disposed on one side (sometimes referred to as the "first side") 10a of the support sheet 10. The support sheet 10 is formed by having a substrate 11 and an adhesive layer 12 disposed on one side (first side) 11a of the substrate 11. In the composite sheet 101 for forming a protective film, the adhesive layer 12 is disposed between the substrate 11 and the protective film forming film 13. That is, the composite sheet 101 for forming the protective film is composed of a substrate 11, an adhesive layer 12 and a protective film forming film 13, which are sequentially stacked along their thickness directions. The first surface 10a of the support sheet 10 is the same surface as the side of the adhesive layer 12 opposite to the side of the substrate 11 (sometimes referred to as the "first surface" in this specification).

[0171] The composite sheet 101 for forming a protective film further comprises an adhesive layer 16 for clamping and a release film 15 on the protective film forming film 13. In the protective film forming composite sheet 101, a protective film forming film 13 is laminated on the entire or almost the entire surface of the first surface 12a of the adhesive layer 12. A clamping adhesive layer 16 is laminated on a portion of the protective film forming film 13 on the side opposite to the adhesive layer 12 (sometimes referred to as the "first surface" in this specification), i.e., near the periphery. Furthermore, a release film 15 is laminated on the area of ​​the first surface 13a of the protective film forming film 13 where the clamping adhesive layer 16 is not laminated, and on the side of the clamping adhesive layer 16 on the side opposite to the protective film forming film 13 (sometimes referred to as the "first surface" in this specification) 16a. A support sheet 10 is provided on the side of the protective film forming film 13 on the side opposite to the first surface 13a (sometimes referred to as the "second surface" in this specification).

[0172] Not limited to the protective film forming composite sheet 101, in the protective film forming composite sheet of this embodiment, the peeling film (e.g., Figure 1 The release film 15 shown is an optional component. The protective film forming composite sheet of this embodiment may or may not have a release film.

[0173] The adhesive layer 16 for the fixture is used to fix the composite sheet 101 for forming the protective film onto a fixture such as a ring frame. The adhesive layer 16 for the fixture may have a single-layer structure containing adhesive components, or it may have a multi-layer structure, wherein the multi-layer structure comprises a sheet as a core material and layers containing adhesive components disposed on both sides of the sheet.

[0174] As described above, when the protective film is formed by the protective film forming film 13, the protective film can be prevented from peeling off from the wafer or chip.

[0175] The protective film forming composite sheet 101 is used in the following manner: with the release film 15 removed, the back side of the wafer is attached to the first side 13a of the protective film forming film 13, and the first side 16a of the fixture adhesive layer 16 is further attached to a fixture such as an annular frame.

[0176] Figure 3 A cross-sectional view is shown to schematically illustrate another example of the composite sheet for forming the protective film of this embodiment. The composite sheet 102 for forming the protective film shown is different in shape and size from the protective film forming film, and the adhesive layer for the clamp is stacked on the first surface of the adhesive layer rather than the first surface of the protective film forming film. Figure 2 The protective film forming composite sheet 101 shown is the same.

[0177] More specifically, in the composite sheet 102 for forming a protective film, the protective film forming film 23 is laminated on a portion of the first surface 12a of the adhesive layer 12, that is, laminated in the width direction of the adhesive layer 12 (in Figure 3 On the central side of the adhesive layer 12 (in the left-right direction). Further, in the area of ​​the first surface 12a of the adhesive layer 12 where the protective film forming film 23 is not laminated, the clamping adhesive layer 16 is laminated from the outside in its width direction in a manner that does not contact or surround the protective film forming film 23. Then, a release film 15 is laminated on the surface of the protective film forming film 23 opposite to the adhesive layer 12 side (sometimes referred to as the "first surface" in this specification) 23a and the first surface 16a of the clamping adhesive layer 16. A support sheet 10 is provided on the surface of the protective film forming film 23 opposite to the first surface 23a (sometimes referred to as the "second surface" in this specification) 23b.

[0178] Figure 4 A cross-sectional view is shown to schematically illustrate another example of the composite sheet for forming the protective film of this embodiment. The protective film forming composite sheet 103 shown here, except that it lacks the adhesive layer 16 for the clamp, is similar to... Figure 3 The protective film forming composite sheet 102 shown is the same.

[0179] Figure 5 A cross-sectional view is shown to schematically illustrate yet another example of the composite sheet for forming the protective film according to this embodiment. The protective film forming composite sheet 104 shown therein, besides having a support sheet 20 instead of the support sheet 10, is also... Figure 2 The protective film forming composite sheet 101 shown is the same.

[0180] The support sheet 20 is composed only of the substrate 11. That is, the composite sheet 104 for forming the protective film is formed by stacking the substrate 11 and the protective film forming film 13 along their thickness direction. The protective film of the support sheet 20 has the same surface (first surface) 20a on the side of the film 13 as the first surface 11a of the substrate 11. The substrate 11 has adhesiveness at least on its first surface 11a.

[0181] The composite sheet for forming the protective film in this embodiment is not limited to... Figures 1-5 The protective film forming composite sheet shown may be modified or deleted without impairing the effects of the present invention. Figures 1-5 The composite sheet shown is a partial composite sheet for forming a protective film, or it may be a composite sheet with additional components added to the composite sheet for forming a protective film described above.

[0182] Next, the various layers that make up the support sheet will be described in detail.

[0183] ○ Substrate The substrate is in sheet or film form, and various resins can be listed as its constituent materials. Examples of resins 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 copolymer, ethylene-(meth)acrylate copolymer, ethylene-(meth)acrylate copolymer, and ethylene-norbornene copolymer; and vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymer. (Resins obtained using vinyl chloride as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate, polyethylene naphthalate, polyethylene butylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalate, and other fully aromatic polyesters in which all structural units have aromatic cyclic groups; copolymers of two or more of the above polyesters; poly(meth)acrylates; polyurethanes; polyurethane acrylates; polyimides; polyamides; polycarbonates; fluoropolymers; polyacetals; modified polyphenylene ethers; polyphenylene sulfides; polysulfones; polyetherketones, etc. Furthermore, examples of the resin include polymer alloys such as mixtures of the polyester and other resins. For polymer alloys of the polyester and other resins, it is preferable that the amount of the resin other than the polyester is relatively small. In addition, the resin may include, for example, a cross-linked resin formed by cross-linking one or more of the resins exemplified above; or a modified resin such as an ionomer of one or more of the resins exemplified above.

[0184] The resin constituting the substrate can be a single type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0185] The substrate can consist of one layer (single layer) or multiple layers (two or more layers). When it consists of multiple layers, these multiple layers can be the same as each other or different from each other. There are no particular restrictions on the combination of these multiple layers.

[0186] The thickness of the substrate is preferably 50–300 μm, more preferably 60–100 μm. By keeping the substrate thickness within the above range, the flexibility and wafer adhesion adaptability of the composite sheet for forming the protective film are further improved. The “thickness of the substrate” refers to the overall thickness of the substrate. For example, the thickness of a substrate composed of multiple layers refers to the total thickness of all the layers that make up the substrate.

[0187] In addition to the main constituent materials such as the resin, the substrate may also contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

[0188] The substrate is preferably transparent, and can be colored according to the purpose, and other layers can also be deposited by vapor deposition. In this embodiment where the protective film forming film has energy-curable properties, the substrate is preferably transmissible to energy rays.

[0189] To adjust the adhesion between the substrate and layers disposed on the substrate (e.g., adhesive layers, protective film forming films, or other layers), the surface can be subjected to surface treatments such as roughening treatment (sandblasting, solvent treatment, etc.); oxidation treatments such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc.; oleophilic treatment; hydrophilic treatment, etc. Furthermore, a primer treatment can be applied to the surface of the substrate.

[0190] The substrate can have adhesiveness on at least one surface by containing a specific range of components (e.g., resins, etc.).

[0191] The substrate can be manufactured using known methods. For example, a resin-containing substrate can be manufactured by molding a resin composition containing said resin.

[0192] ○Adhesive layer The adhesive layer is in sheet or film form and contains adhesive. Examples of adhesives include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyethylene ethers, polycarbonates, ester resins, and other adhesive resins.

[0193] In this specification, "adhesive resin" includes both adhesive resins and bonding resins. For example, the adhesive resin includes not only resins that are adhesive in themselves, but also resins that exhibit adhesiveness when used in conjunction with other components such as additives, or resins that exhibit bonding due to the presence of factors such as heat or water.

[0194] The adhesive layer can consist of one layer (single layer) or multiple layers (two or more layers). When it consists of multiple layers, these multiple layers can be the same as each other or different from each other, and there are no particular restrictions on the combination of these multiple layers.

[0195] The thickness of the adhesive layer is not particularly limited, but it is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm. The "thickness of the adhesive layer" refers to the overall thickness of the adhesive layer. For example, the thickness of an adhesive layer consisting of multiple layers refers to the total thickness of all the layers that make up the adhesive layer.

[0196] The adhesive layer is preferably transparent, but it can also be colored depending on the purpose. In this embodiment where the protective film forming film has energy-curable properties, the adhesive layer is preferably transmissible to energy rays.

[0197] The adhesive layer can be either energy-curable or non-energy-curable. Energy-curable adhesive layers can have their properties adjusted before and after curing. For example, by curing an energy-curable adhesive layer before picking up a chip with a protective film (described later), it becomes easier to pick up the chip with the protective film.

[0198] An adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive layer can be formed at a target location by applying an adhesive composition to the surface to which the adhesive layer is to be formed and drying it as needed. The content ratio between components in the adhesive composition that do not vaporize at room temperature is generally the same as the content ratio between said components in the adhesive layer.

[0199] In the adhesive layer, the total content of one or more of the components described below in the adhesive layer is no more than 100% by mass relative to the total mass of the adhesive layer. Similarly, in the adhesive composition, the total content of one or more of the components described below in the adhesive composition is not greater than 100 by mass relative to the total mass of the adhesive composition.

[0200] The coating and drying of the adhesive composition can be carried out, for example, by the same method as the coating and drying of the composition for forming the protective film described above.

[0201] When applying an adhesive layer to a substrate, it can be done simply by coating the substrate with the adhesive composition and drying it as needed. Alternatively, for example, an adhesive layer can be formed on the release film by coating it with the adhesive composition and drying it as needed, and then the adhesive layer can be laminated onto the substrate by adhering the exposed surface of the adhesive layer to one surface of the substrate. In this case, the release film can simply be removed at any time during the manufacturing process of the composite sheet for forming the protective film or during use.

[0202] When the adhesive layer is energy-curable, examples of energy-curable adhesive compositions include, for example, an adhesive composition (I-1) containing a non-energy-curable adhesive resin (I-1a) (hereinafter sometimes abbreviated as "adhesive resin (I-1a)") and an energy-curable compound; an adhesive composition (I-2) containing an energy-curable adhesive resin (I-2a) (hereinafter sometimes abbreviated as "adhesive resin (I-2a)") with unsaturated groups introduced into the side chains of the non-energy-curable adhesive resin (I-1a); and an adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a) and an energy-curable compound.

[0203] When the adhesive layer is non-energy-curable, examples of non-energy-curable adhesive compositions include adhesive compositions (I-4) containing the non-energy-curable adhesive resin (I-1a).

[0204] [Non-energy radiation-curable adhesive resin (I-1a)] The adhesive resin (I-1a) is preferably an acrylic resin.

[0205] Examples of acrylic resins include acrylic polymers having at least structural units derived from (meth)acrylate alkyl esters. As an example of the alkyl methacrylate, an alkyl methacrylate in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms is provided, wherein the alkyl group is preferably linear or branched.

[0206] In addition to structural units derived from alkyl (meth)acrylates, the acrylic polymer preferably further comprises structural units derived from functionalized monomers. Examples of functionalized monomers include those that form a crosslinking start point by reacting the functional group with a crosslinking agent described later, or those that introduce unsaturated groups into the side chains of acrylic polymers by reacting the functional group with functional groups such as isocyanate groups and glycidyl groups in compounds containing unsaturated groups described later.

[0207] Examples of functional group-containing monomers include hydroxyl-containing monomers, carboxyl-containing monomers, amino-containing monomers, and epoxy-containing monomers.

[0208] In addition to structural units derived from alkyl (meth)acrylates and structural units derived from functionalized monomers, the acrylic polymer may further have structural units derived from other monomers. There are no particular limitations on the other monomers, as long as they can copolymerize with alkyl methacrylates, etc. Other monomers mentioned include, for example, styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

[0209] In the adhesive compositions (I-1), (I-2), (I-3), and (I-4) (hereinafter, these adhesive compositions are collectively referred to as "adhesive compositions (I-1) to (I-4)"), the acrylic polymer and other acrylic resins may have only one structural unit or two or more structural units. When there are two or more structural units, their combination and ratio can be arbitrarily selected.

[0210] In the acrylic polymer, the ratio of the amount of structural units from functional group-containing monomers to the total amount of structural units is preferably 1 to 35 by mass.

[0211] The adhesive composition (I-1) or adhesive composition (I-4) may contain only one type of adhesive resin (I-1a) or two or more types of adhesive resin. When there are two or more types of adhesive resin, the combination and ratio of them can be arbitrarily selected.

[0212] In the adhesive layer formed by the adhesive composition (I-1) or the adhesive composition (I-4), the content of the adhesive resin (I-1a) relative to the total mass of the adhesive layer is preferably 5 to 99% by mass, for example, it can be any range of 25 to 95% by mass, 45 to 95% by mass and 65 to 95% by mass.

[0213] [Energy-curable adhesive resin (I-2a)] The adhesive resin (I-2a) can be obtained, for example, by reacting a compound containing unsaturated groups having energy-ray polymerizable unsaturated groups with the functional groups in the adhesive resin (I-1a).

[0214] The unsaturated group compound is a compound that, in addition to the energy-ray polymerizable unsaturated group, further has a group that can bond with the adhesive resin (I-1a) by reacting with the functional groups in the adhesive resin (I-1a). Examples of polymerizable unsaturated groups that can be used as energy-ray polymerizable groups include (meth)acryloyl, vinyl (ethene), allyl (2-propenyl), etc., with (meth)acryloyl being preferred. Examples of functional groups that can bond with the functional groups in the adhesive resin (I-1a) include isocyanate groups and glycidyl groups that can bond with hydroxyl or amino groups, as well as hydroxyl and amino groups that can bond with carboxyl or epoxy groups.

[0215] Examples of compounds containing unsaturated groups include (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, and (meth)acrylate glycidyl ester.

[0216] The adhesive composition (I-2) or (I-3) may contain only one type of adhesive resin (I-2a) or two or more types of adhesive resin. When there are two or more types of adhesive resin, the combination and ratio of them can be arbitrarily selected.

[0217] In the adhesive layer formed by the adhesive composition (I-2) or (I-3), the content of the adhesive resin (I-2a) relative to the total mass of the adhesive layer is preferably 5 to 99% by mass.

[0218] [Energy-cured compounds] As the energy-curable compound contained in the adhesive composition (I-1) or (I-3), examples include monomers or oligomers that have energy-curable unsaturated groups and can be cured by irradiation with energy rays.

[0219] In energy-curable compounds, monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6- Poly(meth)acrylates such as hexanediol (meth)acrylate; urethane (meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc. In energy-curable compounds, oligomers can be, for example, polymers of monomers as exemplified above.

[0220] The adhesive composition (I-1) or (I-3) may contain only one or more energy-curable compounds, and when there are more than two, their combination and ratio can be arbitrarily selected.

[0221] In the adhesive layer formed by the adhesive composition (I-1) or (I-3), the content of the energy-curable compound relative to the total mass of the adhesive layer is preferably 1 to 95% by mass.

[0222] [Cross-linking agent] When the acrylic polymer having structural units derived from functionalized monomers in addition to structural units derived from alkyl methacrylates is used as the adhesive resin (I-1a), the adhesive composition (I-1) or (I-4) preferably further contains a crosslinking agent. Furthermore, when the acrylic polymer having structural units derived from functional group monomers, for example, the same acrylic polymer as that 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.

[0223] 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 crosslinking agents include isocyanate crosslinking agents (crosslinking agents with isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, phenyl diisocyanate, and adducts of these diisocyanates; epoxy crosslinking agents (crosslinking agents with glycidyl groups) such as ethylene glycol glycidyl ether; aziridinium crosslinking agents (crosslinking agents with aziridinium groups) such as hexa[1-(2-methyl)-aziridinyl]triphosphatriazine; metal chelate crosslinking agents (crosslinking agents with metal chelate structures) such as aluminum chelates; and isocyanurate crosslinking agents (crosslinking agents with isocyanuric acid backbones).

[0224] The crosslinking agent contained in the adhesive compositions (I-1) to (I-4) may be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0225] In the adhesive composition (I-1) or (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the adhesive resin (I-1a), for example, it can be any range of 1 to 40 parts by mass, 5 to 35 parts by mass, and 10 to 30 parts by mass. 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 adhesive resin (I-2a).

[0226] [Photopolymerization initiator] Adhesive compositions (I-1), (I-2), and (I-3) (hereinafter, these adhesive compositions are collectively referred to as "adhesive compositions (I-1) to (I-3)") may further contain a photopolymerization initiator. Adhesive compositions (I-1) to (I-3) containing a photopolymerization initiator can undergo sufficient curing even when irradiated with low-energy rays such as ultraviolet light.

[0227] As the photopolymerization initiator, for example, the same photopolymerization initiator as described above (c) can be listed.

[0228] The photopolymerization initiator contained in the adhesive compositions (I-1) to (I-3) can be only one type or two or more types. When there are two or more types, their combination and ratio can be arbitrarily selected.

[0229] 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 energy-curable compound. In the adhesive composition (I-2), the content of photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of adhesive resin (I-2a). 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-curable compound.

[0230] [Other Additives] Without impairing the effectiveness of this embodiment, the adhesive compositions (I-1) to (I-4) may contain other additives that are not among the above-mentioned components. Other additives mentioned above include, for example, well-known additives such as antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, thickeners, reaction delayers, and crosslinking promoters (catalysts). Furthermore, a reaction delay agent refers to a component that inhibits, for example, the non-targeted crosslinking reaction that occurs in the adhesive compositions (I-1) to (I-4) during storage due to the action of a catalyst incorporated into them. Examples of reaction delay agents include those that form chelate complexes using chelates corresponding to the catalyst; more specifically, reaction delay agents having two or more carbonyl groups (-C(=O)-) in one molecule can be listed.

[0231] The adhesive compositions (I-1) to (I-4) may contain only one other additive or two or more additives. When there are two or more additives, their combination and ratio can be arbitrarily selected.

[0232] The content of other additives in the adhesive compositions (I-1) to (I-4) is not particularly limited; they can be selected appropriately according to their type.

[0233] [solvent] The adhesive compositions (I-1) to (I-4) may contain solvents. By including solvents in the adhesive compositions (I-1) to (I-4), their coating adaptability to the object surface is increased.

[0234] The solvent is preferably an organic solvent. Examples of organic solvents 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; and alcohols such as 1-propanol and 2-propanol.

[0235] The adhesive compositions (I-1) to (I-4) may contain only one solvent or two or more solvents. When there are two or more solvents, their combination and ratio can be arbitrarily selected.

[0236] The solvent content in the adhesive compositions (I-1) to (I-4) is not particularly limited and can be adjusted appropriately.

[0237] ○ Method for preparing adhesive composition Adhesive compositions (I-1) to (I-4) can be obtained by incorporating the adhesive and other components other than the adhesive as needed into the components constituting the adhesive composition. Apart from the difference in the types of admixtures, the adhesive composition can be prepared, for example, by the same method as the protective film forming composition described above.

[0238] ◇Manufacturing method of composite sheet for forming protective film The composite sheet for forming the protective film can be manufactured by stacking the above-described layers in a corresponding positional relationship, and by adjusting the shape of some or all of the layers as needed. The formation methods of each layer are as described above.

[0239] For example, when manufacturing a support sheet, when laminating an adhesive layer on a substrate, it is sufficient to simply apply the adhesive composition to the substrate and dry it as needed. Furthermore, an adhesive layer can also be laminated onto a substrate by coating an adhesive composition onto the release film and drying it as needed to form an adhesive layer on the release film, and then bonding the exposed surface of the adhesive layer to a surface of the substrate. In this case, the adhesive composition is preferably coated on the release-treated surface of the release film. This provides an example of an adhesive layer being laminated on a substrate, but the method described above can also be applied to cases where layers other than the adhesive layer are laminated on a substrate.

[0240] On the other hand, for example, when a protective film is further laminated on an adhesive layer already laminated on a substrate, a protective film forming composition can be applied to the adhesive layer to directly form the protective film forming film. Layers other than the protective film forming film can also be laminated on the adhesive layer using the same method with the composition for forming that layer. Therefore, when forming a new layer (hereinafter referred to as "second layer") on any layer already laminated on the substrate (hereinafter referred to as "first layer") to form a two-layer laminated structure (in other words, a first layer and a second layer laminated structure), a method of applying the composition for forming the second layer to the first layer and drying it as needed can be applied. Preferably, the second layer is formed by pre-forming the composition used to form this layer onto the release film, and then adhering the exposed surface of the second layer, opposite to the side in contact with the release film, to the exposed surface of the first layer, thereby forming a continuous two-layer laminated structure. In this case, it is preferable that the composition is applied to the release treatment surface of the release film. After forming the laminated structure, the release film can be removed as needed. The example given is the case where a protective film is stacked on an adhesive layer to form a film, but any stacking structure can be chosen as the object, such as a stacking structure where layers (films) other than the protective film are stacked on an adhesive layer to form a film.

[0241] Thus, since all layers of the composite sheet constituting the protective film forming material, except for the substrate, can be laminated by pre-forming them on the release film and attaching them to the surface of the target layer, it is only necessary to select the layers that have undergone the above process appropriately to manufacture the composite sheet for forming the protective film.

[0242] Furthermore, protective film forming composite sheets are typically stored with a release film adhered to the surface of the outermost layer (e.g., the protective film forming film) on the side opposite to the support sheet. Therefore, by coating the release film (preferably its peeling surface) with a composition for forming the outermost layer, such as a protective film forming composition, and drying it as needed, a layer constituting the outermost layer is first formed on the release film. Then, by any of the methods described above, the remaining layers are stacked on the exposed surface of this layer on the side opposite to the side in contact with the release film, maintaining the release film adhered to it without removal, thereby obtaining a protective film forming composite sheet with a release film.

[0243] ◇Manufacturing method of chip with protective film (Use of protective film forming film and composite sheet for protective film forming) The protective film forming film and the composite sheet for forming the protective film can be used in the manufacture of the chip with the protective film. That is, a method for manufacturing a chip with a protective film according to one embodiment of the present invention is a method for manufacturing a chip with a protective film comprising a chip and a protective film disposed on the back of the chip. The method for manufacturing a chip with a protective film includes the following steps: a first laminated film formed by attaching the protective film forming film of one embodiment of the present invention to the back of a wafer, thereby forming a first laminated composite film composed of the protective film forming film and the wafer stacked along their thickness directions; or a first laminated composite film formed by attaching the protective film forming film of the protective film forming composite sheet of one embodiment of the present invention to the back of a wafer, thereby forming a first laminated composite film composed of the support sheet, the protective film forming film and the wafer stacked sequentially along their thickness directions (in this specification, it is sometimes referred to as the "attachment step"); and a second laminated film formed by forming the protective film by curing the protective film forming film in the first laminated film or the first laminated composite film with energy rays, thereby forming a second laminated composite film composed of the protective film and the wafer stacked along their thickness directions. The process of fabricating a second laminated composite film, which is formed by sequentially stacking the support sheet, the protective film, and the wafer along their thickness directions (sometimes referred to as the "curing process" in this specification); the process of fabricating a third laminated film by dividing the wafer in the second laminated film and cutting the protective film while a dicing blade is provided on the protective film side of the second laminated film, thereby forming a third laminated composite film on which a plurality of chips with protective films are fixed on the dicing blade, or by dividing the wafer in the second laminated composite film and cutting the protective film, thereby forming a third laminated composite film on which a plurality of chips with protective films are fixed on the support sheet (sometimes referred to as the "division process" in this specification); and the process of picking up the chips with protective films in the third laminated film by pulling them off the dicing blade or the support sheet (sometimes referred to as the "pickup process" in this specification). Hereinafter, with reference to the accompanying drawings, the manufacturing methods of a chip with a protective film when a protective film forming film that does not constitute a composite sheet for forming a protective film is attached to the back of a wafer (in this specification, it is sometimes referred to as "manufacturing method 1") and the manufacturing methods of a chip with a protective film when a protective film forming film in a composite sheet for forming a protective film is attached to the back of a wafer (in this specification, it is sometimes referred to as "manufacturing method 2") will be described in sequence.

[0244] <<Manufacturing Method 1>> Figures 6A-6E This is a cross-sectional view used to schematically illustrate manufacturing method 1. It shows the use of... Figure 1 The protective film 13 shown is illustrated as an example to explain manufacturing method 1. In the attachment process of manufacturing method 1, such as Figure 6AAs shown, a first laminated film 601 is formed by attaching the aforementioned protective film forming film 13 to the back side 9b of the wafer 9. The protective film forming film 13 is attached to a first surface 13a on the back side 9b of the wafer 9. A second release film 152 is provided on a second surface 13b of the protective film forming film 13. Among them, it is shown that from Figure 1 The case shown is where the first release film 151 is removed from the protective film forming film 13, and the first side 13a of the protective film forming film 13 is attached to the back side 9b of the wafer 9. However, it is also possible to remove the first release film 151 from the protective film forming film 13 and attach the first side 13a of the protective film forming film 13 to the back side 9b of the wafer 9. Figure 1 The second release film 152 is removed from the protective film forming film 13 shown, and the second side 13b of the protective film forming film 13 is attached to the back side 9b of the wafer 9.

[0245] The protective film 13 can be attached to the wafer 9 using known methods. For example, the protective film 13 can be attached to the wafer 9 while being heated.

[0246] Next, in the curing step of manufacturing method 1, a protective film 13' is formed by energy-curing the protective film forming film 13 in the first laminated film 601, as shown below. Figure 6B As shown, a second laminated film 602 is thus fabricated, consisting of a protective film 13' and a wafer 9 stacked along their thickness directions. The symbol 13a' denotes the surface of the protective film 13' that previously served as the first surface 13a of the protective film 13 (sometimes referred to as the "first surface" in this specification). The symbol 13b' denotes the protective film 13'... The second surface 13b of the film 13 that was previously used as a protective film (sometimes referred to as the "second surface" in this specification).

[0247] In the curing process, energy rays are irradiated onto the protective film forming film 13 from the outside of the protective film forming film 13 side of the first laminated film 601 through the second release film 152 (transmission second release film 152) to form a protective film 13'. In the curing process, after the second release film 152 is removed from the protective film forming film 13 in the first laminated film 601 to expose the second surface 13b of the protective film forming film 13, the protective film forming film 13' can be formed by irradiating the protective film forming film 13 with energy rays.

[0248] The irradiation conditions of the energy rays in the curing process are as described above.

[0249] By using a protective film to form film 13, the peeling of the protective film 13' from the wafer 9 in the second laminated film 602 obtained in the curing process can be suppressed.

[0250] Next, in the slitting step of manufacturing method 1, the second release film 152 is first removed from the protective film 13' in the second laminated film 602. Then, as... Figure 6C As shown, a side (sometimes referred to as the "first side") 8a of the cutting disc 8 is attached to the second side 13b' of the protective film 13' newly exposed by the above method. The cutting disc 8 shown is composed of a substrate 81 and an adhesive layer 82 disposed on one surface 81a of the substrate 81. The adhesive layer 82 in the cutting disc 8 is attached to a protective film 13'. The surface 82a of the adhesive layer 82 on the protective film 13' side (sometimes referred to as the "first surface" in this specification) is the same as the first surface 8a of the cutting disc 8.

[0251] The cutting disc 8 can be a known cutting disc. For example, the substrate 81 can be the same substrate as the substrate in the composite sheet for forming the protective film described above, and the adhesive layer 82 can be the same adhesive layer as the adhesive layer in the composite sheet for forming the protective film described above. That is, the cutting disc 8 can be the same sheet as the support sheet in the composite sheet for forming the protective film described above.

[0252] The example shown is a cutting disc 8 having a substrate 81 and an adhesive layer 82, but other discs may also be used as cutting discs in the slitting process. For example, a cutting disc consisting only of a substrate may be used.

[0253] Next, in the segmentation process, as Figure 6D As shown, with a dicing blade 8 disposed on the protective film 13' side of the second laminated film 602, the wafer 9 in the second laminated film 602 is divided, and the protective film 13' is cut. Through dicing, the wafer 9 is individualized, thereby forming multiple chips 90.

[0254] The wafer 9 can be diced and the protective film 13' can be cut using known methods. For example, the wafer 9 can be diced and the protective film 13' can be cut continuously by various cutting methods such as blade cutting, laser cutting based on laser irradiation, or water cutting with water jet containing abrasive. Regardless of which of the above cutting methods is used, the protective film 13' is cut along the outer periphery of the chip 90.

[0255] Thus, by dicing the wafer 9 and cutting the protective film 13', multiple chips 901 with protective films can be obtained. Each chip 901 with a protective film has a chip 90 and a cut protective film (sometimes referred to simply as "protective film") 130' disposed on the back side 90b of the chip 90. The symbol 130b' indicates the side of the cut protective film 130' that was previously used as the second side 13b' of the protective film 13' (sometimes referred to as "second side" in this specification).

[0256] In the dicing process of manufacturing method 1, a third laminated film 603 is formed by fixing multiple chips 901 with protective films on the dicing plate 8 in the above manner.

[0257] By using the protective film to form film 13, the protective film 13' can be prevented from peeling off from wafer 9 before and during the dicing process from the start of the dicing process until the third laminated film 603 is obtained, and the protective film 130' can be prevented from peeling off from chip 90.

[0258] Next, in the picking process of manufacturing method 1, as Figure 6E As shown, the chip 901 with a protective film in the third laminate 603 is picked up by pulling it off the cutting disc 8. During the picking process, a peeling occurs between the second side 130b' of the protective film 130' in the chip 901 with the protective film and the first side 82a of the adhesive layer 82 in the dicing die 8.

[0259] The illustration shows the chip 901 with the protective film being pulled away in the direction of arrow P using a pull-away tool 7 such as a vacuum collet. A cross-sectional view of the pull-away tool 7 is omitted here. The chip 901 with the protective film can be picked up using known methods.

[0260] When the adhesive layer 82 is energy-curable, it is preferable that, in the pick-up process, the adhesive layer 82 is cured by irradiating it with energy rays to form a cured product (not shown), and then the chip 901 with the protective film is pulled away from the cutting disc 8. At this time, in the pick-up process, peeling occurs between the protective film 130' in the chip 901 with the protective film and the cured product of the adhesive layer 82 in the cutting disc 8. At this time, since the adhesion between the cured adhesive layer 82 and the protective film 130' is less than the adhesion between the adhesive layer 82 and the protective film 130', it is easier to pick up the chip 901 with the protective film.

[0261] The irradiation conditions for the adhesive layer 82 in the picking process can be, for example, the same as the irradiation conditions for the protective film forming film 13 in the curing process.

[0262] In this specification, as long as the laminated structure between the substrate and the cured product of the energy-curable adhesive layer is maintained, the laminated structure will still be referred to as a "cutting disc" even after the energy-curable adhesive layer has undergone energy-curing.

[0263] On the other hand, when the adhesive layer 82 is non-energy-curable, the chip 901 with the protective film can be directly pulled off the adhesive layer 82 without curing, thus the chip 901 with the protective film can be picked up with a simplified process. Even if the adhesive layer 82 is energy-curable, the chip 901 with the protective film can be picked up without curing the adhesive layer 82, thus picking up the chip 901 with the protective film in a simplified process.

[0264] In the picking process, all the target chips 901 with protective films can be picked up.

[0265] By using a protective film to form film 13, the protective film 130' can be prevented from peeling off from chip 90 during the period from the start to the end of the picking process, whether before or after picking.

[0266] In manufacturing method 1, by proceeding to the picking process, a chip 901 with a protective film can be obtained as the target.

[0267] Thus far, the following situation has been explained: after the first laminate is fabricated, a protective film is formed by energy beam curing of the protective film forming film in the first laminate, a second laminate is fabricated, and then a dicing blade is attached to the protective film in the second laminate to cleave the wafer and cut the protective film. That is, the case where the curing process is performed after the attachment process, then the dicing blade is attached to the object to be attached (here, the protective film), and then the cleaving process is performed has been explained. However, in manufacturing method 1, the timing of attaching the dicing blade to the object to be attached is not limited to this. For example, in manufacturing method 1, after the first laminated film is fabricated, a dicing disc can be attached to the protective film forming film in the first laminated film. The resulting first laminated film with the dicing disc (which may also be a first laminated film with a support sheet, depending on the situation) is then subjected to energy-ray curing of the protective film forming film to form a protective film, thereby fabricating a second laminated film. The wafer in the second laminated film is then diced, and the protective film is cut. That is, after the attachment step, the dicing disc can be attached to the attachment object (here, the protective film forming film), the resulting first laminated film with the dicing disc (which may also be a first laminated film with a support sheet, depending on the situation) can be subjected to the curing step, and then the dicing step can be performed. The first laminated film with the support sheet is the same as the first laminated composite film described later. A cross-sectional view illustrating manufacturing method 1 in this manner is shown in [the image / image / etc.]. Figures 7A to 7E .

[0268] <<Manufacturing Method 2>> Figures 8A to 8D This is a cross-sectional view used to schematically illustrate manufacturing method 2. It shows the use of... Figure 2 The case of the protective film forming composite sheet 101 is shown as an example to illustrate manufacturing method 2. In the attachment process of manufacturing method 2, such as Figure 8A As shown, a first laminated composite sheet 501 is fabricated by attaching a protective film forming film 13 from a protective film forming composite sheet 101 to the back side 9b of the wafer 9. This first laminated composite sheet 501 is composed of a support sheet 10, a protective film forming film 13, and the wafer 9, which are sequentially stacked along their thickness directions. At this time, similar to manufacturing method 1, the first surface 13a of the protective film forming film 13 from the protective film forming composite sheet 101 is attached to the back side 9b of the wafer 9.

[0269] The protective film forming film 13 in the protective film forming composite 101 can be attached to the wafer 9 using known methods. For example, the protective film forming film 13 can be attached to the wafer 9 while being heated.

[0270] Next, in the curing step of manufacturing method 2, the protective film forming film 13 in the first laminated composite sheet 501 is cured by energy rays to form a protective film 13', as shown below. Figure 8B As shown, a second laminated composite sheet 502 is thus fabricated, which is composed of a support sheet 10, a protective film 13' and a wafer 9 stacked sequentially along their thickness directions.

[0271] In the curing process, energy rays are irradiated onto the protective film forming film 13 from the outside of the support sheet 10 side of the first laminated composite sheet 501 through the support sheet 10 (transmission support sheet 10) to form the protective film 13'.

[0272] Except for using a first laminated composite sheet 501 instead of a first laminated film 601, the curing process can be performed in the same manner as the curing process in manufacturing method 1.

[0273] The second laminated composite sheet 502 obtained in the curing process has the same structure as the laminate of the second laminated film 602 and the cutting sheet 8 in the slitting process of 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.

[0274] By using the protective film forming film 13, the protective film 13' in the second laminated composite sheet 502 obtained in the curing process can be prevented from peeling off from the wafer 9.

[0275] Next, in the dividing process of manufacturing method 2, as... Figure 8C As shown, the wafer 9 in the second-layer composite 502 is divided, and the protective film 13' is cut off. Through division, the wafer 9 is monolithized, thereby forming multiple chips 90.

[0276] Except for using a second laminated composite sheet 502 to replace the laminate of the second laminated film 602 and the cutting sheet 8, the slitting process can be performed in the same manner as the slitting process in manufacturing method 1. In manufacturing method 2, regardless of the cutting method, the protective film 13' is cut along the outer periphery of the chip 90.

[0277] Thus, by dividing the wafer 9 and cutting the protective film 13', a plurality of chips 901 with protective films can be obtained. Each chip 901 with a protective film has a chip 90 and a cut protective film 130' disposed on the back side 90b of the chip 90. The chips 901 with protective films obtained in the dicing process of manufacturing method 2 are the same as the chips 901 with protective films obtained in the dicing process of manufacturing method 1.

[0278] In the above manner, during the slitting process of manufacturing method 2, a third-layer composite sheet 503 is formed by fixing multiple chips 901 with protective films on the support sheet 10. The third laminated composite sheet 503 has the same structure as the third laminated film 603 obtained in the slitting process of manufacturing method 1. When the cutting sheet 8 and the support sheet 10 are the same, the third laminated composite sheet 503 is the same as the third laminated film 603.

[0279] By using the protective film to form film 13, during the period from the start of the dicing process to the obtaining of the third laminated composite 503, the protective film 13' can be prevented from peeling off from wafer 9 before and during dicing, and the protective film 130' can be prevented from peeling off from chip 90.

[0280] Next, in the picking process of manufacturing method 2, as Figure 8D As shown, the chip 901 with a protective film in the third-layer composite sheet 503 is picked up by pulling it away from the support sheet 10. During the picking process, a peeling occurs between the second side 130b' of the protective film 130' in the chip 901 with the protective film and the first side 12a of the adhesive layer 12 in the support sheet 10.

[0281] Except for using a third laminated composite sheet 503 instead of a third laminated film 603, the picking process can be performed in the same way as the picking process in manufacturing method 1.

[0282] For example, when the adhesive layer 12 is energy-curable, in the pickup process, it is preferable to cure the adhesive layer 12 by irradiating it with energy rays to form a cured product (not shown), and then separate the chip 901 with the protective film from the support sheet 10. At this time, in the pickup process, peeling occurs between the protective film 130' in the chip 901 with the protective film and the cured product of the adhesive layer 12 in the support sheet 10. At this time, since the adhesion between the cured adhesive layer 12 and the protective film 130' is less than the adhesion between the adhesive layer 12 and the protective film 130', it is easier to pick up the chip 901 with the protective film.

[0283] On the other hand, when the adhesive layer 12 is non-energy-curable, the chip 901 with the protective film can be directly pulled off the adhesive layer 12 without curing, so the chip 901 with the protective film can be picked up with a simplified process. Even if the adhesive layer 12 is energy-curable, the chip 901 with the protective film can be picked up without curing the adhesive layer 12, thus picking up the chip 901 with the protective film in a simplified process.

[0284] By using a protective film to form film 13, the protective film 130' can be prevented from peeling off from chip 90 during the period from the start to the end of the picking process, whether before or after picking.

[0285] In manufacturing method 2, by proceeding to the picking step, a chip 901 with a protective film as the target can be obtained. The chip 901 with a protective film obtained in manufacturing method 2 is the same as the chip 901 with a protective film obtained in manufacturing method 1.

[0286] At this point, the use of Figure 2 The manufacturing method 2 for forming the protective film composite sheet 101 shown has been described. In manufacturing method 2, another method can also be used. Figures 3-5 The protective film forming composite sheets of this embodiment, other than the protective film forming composite sheet 101, are shown as protective film forming composite sheet 102, protective film forming composite sheet 103, or protective film forming composite sheet 104.

[0287] ◇Manufacturing method of substrate device (Usage method of chip with protective film) After obtaining a chip with a protective film through the above manufacturing method, the substrate device can be manufactured using the same method as the conventional substrate device manufacturing method, except that the chip with the protective film is used instead of the conventional chip with the protective film.

[0288] As a method for manufacturing the substrate device, for example, a manufacturing method having a flip-chip interconnection process can be cited. This flip-chip interconnection process involves contacting the protruding electrodes on a chip with a protective film formed using the protective film with the connection pads on a circuit board, thereby electrically connecting the protruding electrodes to the connection pads on the circuit board.

[0289] By using the protective film formed in this embodiment, the peeling of the protective film from the chip in the substrate device can be suppressed. Therefore, this substrate device is superior to conventional substrate devices in terms of high reliability. Example

[0290] The present invention will now be described in more detail through specific embodiments. However, the present invention is not limited to any of the embodiments shown below.

[0291] <Raw Materials for Resin Preparation> The following shows the formal names of the raw materials for preparing the resin, which are abbreviated in this embodiment and comparative example. BA: n-Butyl acrylate MA: Methyl acrylate ACrMO: 4-Acryloylmorpholine HEA: 2-Hydroxyethyl acrylate 2EHMA: 2-Ethylhexyl methacrylate

[0292] <Raw materials for preparing the composition for protective film formation> The following are the raw materials used to prepare compositions for forming protective films. [Energy-based solidification component (a)] (a)-1: Carbamate acrylate (“Quick cure8100EA70” manufactured by KJ Chemicals Corporation) (a)-2: ε-caprolactone-modified tri-(2-acryloyloxyethyl)isocyanurate ("A-9300-1CL" manufactured by SHIN-NAKAMURACHEMICAL CO.,LTD., a 3-functional UV-curable compound) [Acrylic resin without energy-curing groups (b)] (b)-1: An acrylic resin (weight average molecular weight of 700,000 and glass transition temperature of 2°C) that is a copolymer of BA (33 parts by mass), MA (27 parts by mass), ACrMO (25 parts by mass) and HEA (15 parts by mass). (b)-2: Acrylic resin (weight average molecular weight of 700,000 and glass transition temperature of -8°C) as a copolymer of BA (35 parts by mass), MA (35 parts by mass), ACrMO (15 parts by mass) and HEA (15 parts by mass). [Photopolymerization initiator (c)] (c)-1: 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (BASF's "Omnirad 369"). (c)-2: 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one (BASF's "Omnirad 127D") [Inorganic filler material (d)] (d)-1: Silica filler (fused silica filler, average particle size 8μm) [Coloring agent (g)] (g)-1: Black pigment (a pigment prepared by mixing 32 parts by mass of phthalocyanine blue pigment (Pigment Blue 15:3), 18 parts by mass of isoindolinone yellow pigment (Pigment Yellow 139), and 50 parts by mass of anthraquinone red pigment (Pigment Red 177) such that the total amount of the three pigments / the amount of styrene-acrylic resin = 1 / 3 (mass ratio).) [General Additives (z)] (z)-1: Hydroxyphenyl triazine UV absorber ("Tinuvin 479" manufactured by BASF) [Other polymers that do not possess energy-curing groups (b0)] (b0)-1: An acrylic resin (weight average molecular weight of 700,000 and glass transition temperature of 2°C) that is a copolymer of BA (11 parts by mass), MA (69 parts by mass), ACrMO (5 parts by mass) and HEA (15 parts by mass). (b0)-2: An acrylic resin (weight average molecular weight of 700,000 and glass transition temperature of 6°C) that is a copolymer of MA (85 parts by mass) and HEA (15 parts by mass).

[0293] <<Protective Film Formation and Manufacturing of Chips with Protective Films>> [Example 1] <Preparation of protective film forming composition (IV)-1> The energy-curable component (a)-1 (10.1 parts by mass), the energy-curable component (a)-2 (12.4 parts by mass), the acrylic resin (b)-1 (14.7 parts by mass) without energy-curable groups, the photopolymerization initiator (c)-1 (0.1 parts by mass), the photopolymerization initiator (c)-2 (0.5 parts by mass), the inorganic filler (d)-1 (58.4 parts by mass), the colorant (g)-1 (3 parts by mass), and the general additive (z)-1 (0.8 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain an energy-curable protective film forming composition (IV)-1 with a total concentration of 45% by mass for all components except the solvent. Furthermore, the amounts of components other than the solvent shown here are the amounts of the target material without solvent.

[0294] <Manufacturing of Protective Film Formation> Using a release film (second release film, "SP-PET382150" manufactured by LINTEC Corporation, with a thickness of 38 μm) that has undergone single-sided release treatment on a silicone-treated polyethylene terephthalate film, the above-mentioned protective film forming composition (IV)-1 is coated on the release-treated surface and dried at 100°C for 2 minutes, thereby producing an energy-curable protective film forming film with a thickness of 25 μm.

[0295] Furthermore, on the exposed surface of the obtained protective film forming film that does not have the second release film, the release treatment surface of the release film (the first release film, "SP-PET381031" manufactured by LINTEC Corporation, with a thickness of 38μm) is attached, thereby obtaining a protective film forming film with a release film, which is composed of a protective film forming film, a first release film disposed on one side of the protective film forming film, and a second release film disposed on the other side of the protective film forming film.

[0296] <Preparation of Adhesive Composition (I-4)-1> A non-energy-curable adhesive composition (I-4)-1 is prepared, comprising acrylic resin (100 parts by weight), toluene diisocyanate crosslinking agent (“BHS8515” manufactured by TOYOCHEM CO.,LTD.) (10 parts by weight based on crosslinking agent content), hexamethylene diisocyanate crosslinking agent (“CORONATE HL” manufactured by Tosoh Corporation) (7.5 parts by weight based on crosslinking agent content), and further comprising methyl ethyl ketone as a solvent. The acrylic resin is a copolymer with a weight average molecular weight of 600,000, copolymerized from 2EHMA (80 parts by weight) and HEA (20 parts by weight).

[0297] <Manufacturing of the Support Sheet> Using a release film ("SP-PET381031", manufactured by LINTEC Corporation, with a thickness of 38 μm) that has undergone single-sided release treatment on a silicone-treated polyethylene terephthalate film, the adhesive composition (I-4)-1 obtained above is coated on the release-treated surface, and the film is heated and dried at 100°C for 2 minutes, thereby forming a non-energy-curable adhesive layer with a thickness of 5 μm. Next, a polypropylene film (80 μm thick, colorless) is laminated onto the exposed surface of the adhesive layer as a substrate, thereby creating a support sheet with a release film, which is composed of a substrate, an adhesive layer and a release film stacked sequentially along their thickness directions.

[0298] <Manufacturing of Chips with Protective Film> Using an adhesive tape bonding device ("Adwill RAD-3600F / 12" manufactured by LINTEC Corporation), the first and second release films are removed from the protective film formed above. Under the conditions of a bonding temperature of 70°C, a bonding pressure of 0.3 MPa, and a bonding speed of 50 mm / s, a newly generated exposed surface of the protective film is thermally laminated onto the #2000 polished surface of an 8-inch silicon wafer (thickness of 350 μm), thereby attaching the protective film to the silicon wafer (attachment process). This produces the first laminated film.

[0299] Remove the release film from the support sheet obtained above. Then, using an adhesive tape bonding device ("Adwill RAD-2700" manufactured by LINTEC Corporation), fix the first laminated film, which is fixed to the device, to the annular frame. Then, under the conditions of bonding pressure of 0.3 MPa and bonding speed of 20 mm / s, laminate the exposed surface of the adhesive layer obtained by removing the release film with the exposed surface of the protective film forming film, and attach the support sheet to the protective film forming film in the first laminated film (bonding process). The first laminated film with the support sheet is thus produced.

[0300] Next, for the first laminated film with the support sheet, an ultraviolet irradiation device (LINTEC Corporation's "RAD2000m / 8") was used at an illuminance of 200 mW / cm². 2 The light intensity is 300 mJ / cm² 2 Under certain conditions, the protective film is irradiated twice with ultraviolet light through the substrate and adhesive layer, thereby curing the protective film and forming a protective film (curing process). This process is then used to produce the second laminated film.

[0301] Next, in the second layer, a dicing device (DISCO Corporation's "DFD6362") is used to dice the silicon wafer into 3mm × 3mm silicon chips. Simultaneously, the protective film is cut along the outer periphery of the silicon chips, creating multiple chips with protective films (dicing process). This creates a third layer consisting of multiple silicon chips with protective films fixed on a support substrate. These silicon chips with protective films, along with the wafer, are dried at 125°C for 24 hours.

[0302] Next, the silicon chip with the protective film in the third layer of the film is pulled off the support sheet and picked up (picking process). Thus, the chip with a protective film, which serves as the target, is obtained.

[0303] [Example 2] <Preparation of protective film forming composition (IV)-2> Except that acrylic resin (b)-2 (14.7 parts by mass) without energy-curable groups is used instead of acrylic resin (b)-1 (14.7 parts by mass) without energy-curable groups, protective film forming composition (IV)-2 is prepared by the same method as that used in Example 1 for preparing protective film forming composition (IV)-1.

[0304] <Making of Protective Film Forming Film and Chips with Protective Film> Except that protective film forming composition (IV)-2 is used instead of protective film forming composition (IV)-1, the protective film forming film is manufactured in the same manner as in Example 1. Next, except that the protective film is used to form the film, the chip with the protective film is manufactured in the same way as in Example 1.

[0305] [Example 3] <Preparation of protective film forming composition (IV)-3> Except that the amount of energy-curable component (a)-1 is set to 14.4 parts by mass instead of 10.1 parts by mass, and the amount of acrylic resin (b)-1 without energy-curable groups is set to 10.4 parts by mass instead of 14.7 parts by mass, the protective film forming composition (IV)-3 is prepared by the same method as the protective film forming composition (IV)-1 prepared in Example 1.

[0306] <Making of Protective Film Forming Film and Chips with Protective Film> Except that protective film forming composition (IV)-3 is used instead of protective film forming composition (IV)-1, the protective film forming film is manufactured in the same manner as in Example 1. Next, except that the protective film is used to form the film, the chip with the protective film is manufactured in the same way as in Example 1.

[0307] [Example 4] <Preparation of protective film forming composition (IV)-4> Except that the amount of energy-curable component (a)-1 is set to 14.4 parts by mass instead of 10.1 parts by mass, and acrylic resin (b)-2 (10.4 parts by mass) without energy-curable groups is added instead of acrylic resin (b)-1 (14.7 parts by mass) without energy-curable groups, protective film forming composition (IV)-4 is prepared by the same method as that used in Example 1 for preparing protective film forming composition (IV)-1.

[0308] <Making of Protective Film Forming Film and Chips with Protective Film> Except that protective film forming composition (IV)-4 is used instead of protective film forming composition (IV)-1, the protective film forming film is manufactured in the same manner as in Example 1. Next, except that the protective film is used to form the film, the chip with the protective film is manufactured in the same way as in Example 1.

[0309] [Comparative Example 1] <Preparation of protective film forming composition (X)-1> Except that a polymer (b0)-1 (14.7 parts by mass) without energy-curable groups is used instead of acrylic resin (b)-1 (14.7 parts by mass) without energy-curable groups, the protective film forming composition (X)-1 is prepared by the same method as the protective film forming composition (IV)-1 prepared in Example 1.

[0310] <Making of Protective Film Forming Film and Chips with Protective Film> Except that protective film forming composition (X)-1 is used instead of protective film forming composition (IV)-1, the protective film forming film is manufactured in the same manner as in Example 1. Next, except that the protective film is used to form the film, the chip with the protective film is manufactured in the same way as in Example 1.

[0311] [Comparative Example 2] <Preparation of protective film forming composition (X)-2> Except that the amount of energy-curable component (a)-1 is set to 17.5 parts by mass instead of 10.1 parts by mass, and the amount of acrylic resin (b)-1 without energy-curable groups is set to 7.3 parts by mass instead of 14.7 parts by mass, the protective film forming composition (X)-2 is prepared by the same method as the protective film forming composition (IV)-1 prepared in Example 1.

[0312] <Making of Protective Film Forming Film and Chips with Protective Film> Except that protective film forming composition (X)-2 is used instead of protective film forming composition (IV)-1, the protective film forming film is manufactured in the same manner as in Example 1. Note that, except for the use of this protective film to form the film, the chip with the protective film is manufactured in the same way as in Example 1.

[0313] [Comparative Example 3] <Preparation of protective film forming composition (X)-3> Except that the amount of energy-curable component (a)-1 is set to 17.5 parts by mass instead of 10.1 parts by mass, and acrylic resin (b)-2 (7.3 parts by mass) without energy-curable groups is added instead of acrylic resin (b)-1 (14.7 parts by mass) without energy-curable groups, the protective film forming composition (X)-3 is prepared by the same method as the protective film forming composition (IV)-1 prepared in Example 1.

[0314] <Making of Protective Film Forming Film and Chips with Protective Film> Except that protective film forming composition (X)-3 is used instead of protective film forming composition (IV)-1, the protective film forming film is manufactured in the same manner as in Example 1. Next, except that the protective film is used to form the film, the chip with the protective film is manufactured in the same way as in Example 1.

[0315] [Comparative Example 4] <Preparation of protective film forming composition (X)-4> Except that the amount of energy-curable component (a)-1 is set to 14.4 parts by mass instead of 10.1 parts by mass, and other polymers (b0)-1 (10.4 parts by mass) without energy-curable groups are incorporated instead of acrylic resin (b)-1 (14.7 parts by mass) without energy-curable groups, protective film forming composition (X)-4 is prepared by the same method as that used in Example 1 for preparing protective film forming composition (IV)-1.

[0316] <Making of Protective Film Forming Film and Chips with Protective Film> Except that protective film forming composition (X)-4 is used instead of protective film forming composition (IV)-1, the protective film forming film is manufactured in the same manner as in Example 1. Next, except that the protective film is used to form the film, the chip with the protective film is manufactured in the same way as in Example 1.

[0317] [Comparative Example 5] <Preparation of protective film forming composition (X)-5> Except that a polymer (b0)-2 (14.7 parts by mass) without energy-curable groups is used instead of acrylic resin (b)-1 (14.7 parts by mass) without energy-curable groups, the protective film forming composition (X)-5 is prepared by the same method as the protective film forming composition (IV)-1 prepared in Example 1.

[0318] <Making of Protective Film Forming Film and Chips with Protective Film> Except that protective film forming composition (X)-5 is used instead of protective film forming composition (IV)-1, the protective film forming film is manufactured in the same manner as in Example 1. Next, except that the protective film is used to form the film, the chip with the protective film is manufactured in the same way as in Example 1.

[0319] <<Evaluation of Protective Film Formation>> <Evaluation of the peel inhibition effect of the protective film> For each embodiment and comparative example, a total of 25 silicon chips with protective films obtained above were stored for 7 days at a temperature of 85°C and a relative humidity of 85%. Then, the stored silicon chips with protective films were heat-treated at 260°C for 10 minutes using a reflow oven. Furthermore, the 25 silicon chips with protective films after heat treatment were subjected to the following temperature cycling test: a total of 1000 cycles of cooling at -40°C for 10 minutes followed by heating at 125°C for 10 minutes. Then, for the 25 silicon chips with protective films after the temperature cycling test, the number N (where N is an integer from 0 to 25) of silicon chips with protective films that did not show any peeling from the silicon chips was confirmed using a SAT apparatus (SONOSCAN, INC. "D9600 CSAM"). Next, the peeling inhibition effect of the protective film was evaluated according to the following criteria. The results are shown in Table 1 or Table 2. "N / 25" is recorded in the corresponding column of Table 1 and Table 2. A: N is 25. B: N is 23-24. C: N is below 22.

[0320] The "-" in the ingredient list of Tables 1 and 2 indicates that the protective film forming film does not contain that ingredient.

[0321] <Determination of the storage modulus of the protective film> For each embodiment and comparative example, the protective film forming film with multiple release films obtained above was used to remove their first or second release films and at the same time the exposed surfaces of the protective film forming films were bonded together to produce a test piece (protective film forming film test piece) as a stack of multiple protective film forming films (thickness of 200 μm, length in the stretching direction of the stretching mode described later is 30 mm). Next, using an automated dynamic viscoelasticity measuring device ("RHEOVIBRONDDV-01FP" manufactured by A&D Company, Limited), the storage modulus E' of the protective film forming test piece was measured under the following conditions: tensile method (tensile mode), clamp distance of 20 mm, amplitude of 5 μm, frequency of 11 Hz, and constant temperature rise of 3 °C / min. The temperature range was -10 °C to 140 °C.

[0322] <Determination of the storage modulus of the protective film> For each embodiment and comparative example, the protective film forming film with multiple release films obtained above is used to remove their first or second release films and simultaneously bond the exposed surfaces of the protective film forming films together, thereby producing a stack of multiple protective film forming films (thickness 50 μm). Next, an ultraviolet irradiation device (LINTEC Corporation's "RAD2000m / 8") was used with an illuminance of 200 mW / cm². 2 The light intensity is 300 mJ / cm² 2 Under the specified conditions, the laminate is irradiated twice with ultraviolet light from both sides, thereby curing the protective film. After obtaining a laminate of multiple protective films in the above manner, its width is made into 5 mm, thereby producing a test piece (protective film test piece) (thickness of 50 μm, length in the stretching direction of the stretching mode described later is 30 mm). Next, using a dynamic mechanical analysis device (TA Instruments' "DMA Q800"), the storage modulus E' of the protective film test piece was measured in the temperature range of 0℃ to 300℃ under the following conditions: tensile method (tensile mode), clamp distance of 20mm, amplitude of 5μm, frequency of 11Hz, and constant temperature rise of 3℃ / min.

[0323] [Table 1]

[0324] [Table 2]

[0325] The results above show that in Examples 1 to 4, the peeling of the protective film from the silicon chip was significantly suppressed, especially in Examples 1 to 3, where the effect was high. The protective film forming films of Examples 1 to 4 contain an acrylic resin (b) without energy-curable groups, wherein the proportion of structural units derived from ACrMO in the acrylic resin (b) without energy-curable groups relative to the total amount of structural units (referred to as "proportion of structural units derived from ACrMO in the acrylic resin (b) without energy-curable groups (mass %)" in Tables 1 and 2) is 15% by mass or more, and in these protective film forming films, the content of said acrylic resin (b) relative to the total mass of the protective film forming film is 10.4% by mass or more.

[0326] The storage modulus E' of the protective film forming film test piece at 70°C 70 The pressures of 1.2 MPa (Example 1), 1 MPa (Example 2), 6 MPa (Example 3), and 5.5 MPa (Example 4) all exhibit excellent properties in wafer mounting. Furthermore, in the silicon chips with protective films in Examples 1 to 4, there are virtually no gaps between the protective film and the silicon chip, resulting in high adhesion between the protective film and the silicon chip.

[0327] The storage modulus E' of the protective film test piece at 130°C 130 In Examples 1-4, the pressure was 20 MPa, and all of them exhibited excellent properties as a protective film.

[0328] However, in Comparative Examples 1 to 5, the effect of inhibiting the protective film from peeling off the silicon chip was low, especially in Comparative Example 5. Although the protective film forming films of Comparative Examples 2 and 3 contain acrylic resin (b) in which the amount of structural units derived from ACrMO is more than 15% by mass relative to the total amount of structural units and does not have energy-curable groups, the content of said acrylic resin (b) in these protective film forming films is 7.3% by mass relative to the total mass of the protective film forming film. The protective film formed in Comparative Examples 1, 4, and 5 does not contain the acrylic resin (b), but instead contains other polymers (b0) that do not have energy-curable groups. Furthermore, in these other polymers (b0), the proportion of structural units derived from ACrMO relative to the total amount of structural units (referred to in Tables 1 and 2 as "proportion of structural units derived from ACrMO in other polymers (b0) that do not have energy-curable groups (mass %)") is 5% by mass or less. Industrial applicability

[0329] This invention can be used in the manufacture of various substrate devices, primarily semiconductor devices.

Claims

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) that does not have energy-curable groups. The acrylic resin (b) has structural units derived from 4-(meth)acryloylmorpholine. In the acrylic resin (b), the amount of the structural unit derived from 4-(meth)acryloylmorpholine is 23% to 30% by mass relative to the total amount of structural units. In the protective film forming membrane, the content of the acrylic resin (b) relative to the total mass of the protective film forming membrane is more than 10% by mass and less than 25% by mass.

2. The protective film forming film according to claim 1, wherein, The protective film forming film further contains a multifunctional urethane (meth) acrylate oligomer as an energy ray curable component (a).

3. A composite sheet for forming a protective film, comprising a support sheet and a protective film forming film disposed on one surface of the support sheet. The protective film forming membrane is the protective film forming membrane as described in claim 1 or 2.

4. A method for manufacturing a chip with a protective film, comprising a chip and a protective film disposed on the back of the chip, wherein... The manufacturing method of the chip with the protective film includes the following steps: The process of fabricating a first laminated film consisting of the protective film forming film and the wafer stacked along their thickness directions by attaching the protective film forming film as described in claim 1 or 2 to the back of the wafer, or the process of fabricating a first laminated composite sheet consisting of the support sheet, the protective film forming film and the wafer stacked sequentially along their thickness directions by attaching the protective film forming film from the protective film forming composite sheet as described in claim 3 to the back of the wafer. The protective film is formed by energy ray curing of the protective film forming film in the first laminated film or the first laminated composite sheet, and a second laminated film is formed by laminating the protective film and the wafer along their thickness direction, or a second laminated composite sheet is formed by laminating the support sheet, the protective film and the wafer in sequence along their thickness direction. With a dicing blade disposed on the protective film side of the second laminated film, a third laminated film is fabricated by dividing the wafer in the second laminated film and cutting the protective film, thereby fixing multiple chips with protective films onto the dicing blade; or a third laminated composite film is fabricated by dividing the wafer in the second laminated composite film and cutting the protective film, thereby fixing multiple chips with protective films onto a support sheet; and The process involves picking up the chip with the protective film from the cutting sheet or from the support sheet in the third laminated composite film.

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