TWI895380B - Film adhesive and dicing adhesive - Google Patents

Abstract

The film-like adhesive 13 of the present invention is a curable film-like adhesive 13. For a first test piece having a thickness of 200 μm and being a laminate of multiple sheets of the film-like adhesive 13, in accordance with JIS K7128-3, the distance between a pair of clamps holding and securing the first test piece is set to 60 mm, and the tearing speed is set to 200 mm/min. When a tear test is performed using the right-angle tear method, the displacement of the first test piece in the tearing direction from the time the tear strength of the first test piece reaches its maximum until the first test piece breaks is less than 15 mm.

Description

Film adhesive and dicing adhesive

This invention relates to a film adhesive and a dicing adhesive wafer. This application claims priority based on Japanese Patent Application No. 2020-048261 filed in Japan on March 18, 2020, and the contents of that application are incorporated herein by reference.

A semiconductor chip is typically die-bonded to the circuit-forming surface of a substrate using a film-like adhesive (sometimes called a "die-bond film") applied to the inner surface of the semiconductor chip. Subsequently, one or more semiconductor chips are stacked on top of the semiconductor chip as needed, wire-bonded, and sealed with a resin to create a semiconductor package. This semiconductor package is then used to manufacture the desired semiconductor device.

Semiconductor chips with a film adhesive on the inside are produced, for example, by dividing a semiconductor wafer with a film adhesive on the inside and also cutting the film adhesive. As a method of dividing a semiconductor wafer into semiconductor chips in this way, for example, a method of using a dicing blade to cut the semiconductor wafer together with the film adhesive is widely used. In this case, the film adhesive before cutting is layered on a support sheet (sometimes also called a "dicing sheet") used to fix the semiconductor wafer during cutting and formed into a whole to be used as a cutting adhesive chip. After the cutting is completed, the semiconductor chip with the film adhesive on the inside after the cut (semiconductor chip with a film adhesive) is pulled off the support sheet and picked up.

During pickup, the film adhesive must be pulled away from the support sheet along with the semiconductor chip. For example, if the film adhesive's adhesion to the support sheet is too strong, it becomes difficult to pick up the semiconductor chip with the film adhesive, and the film adhesive peels off the semiconductor chip, leaving residue on the support sheet. If the frequency of such film adhesive residue is high, it not only causes process failures but also increases the manufacturing cost of the semiconductor device.

In contrast, a dicing-and-bonding integrated tape (equivalent to the aforementioned dicing-and-bonding wafer) is disclosed. It comprises a base layer, an adhesive layer, and an adhesive layer (equivalent to the aforementioned film-like adhesive) stacked in sequence. The adhesive layer's elongation at break is regulated within a specific range before and after irradiation with an electron beam, ultraviolet light, or visible light (see Patent Document 1). Using this dicing-and-bonding integrated tape allows for efficient pickup of semiconductor chips with film-like adhesives, even while reducing the force applied to the semiconductor chips during pickup. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2015-126217.

[The problem that the invention aims to solve]

However, in order to improve the pickup suitability of semiconductor chips with film adhesives, the dicing-bonding tape described in Reference 1 requires a support sheet having an adhesive layer in direct contact with the film adhesive, and the selection of the support sheet is limited.

The present invention aims to provide a film adhesive and a dicing wafer equipped with the film adhesive. The film adhesive can be laminated with a support sheet to form a dicing wafer. Even without the need for a support sheet with an adhesive layer in direct contact with the film adhesive, the film adhesive can be prevented from remaining on the support sheet when picking up a semiconductor wafer equipped with the film adhesive. [Means for Solving the Problem]

The present invention provides a film-like adhesive, which is a curable film-like adhesive. For a first test piece, which is a laminate of multiple sheets of the film-like adhesive and has a thickness of 200 μm, the distance between a pair of clamps holding and securing the first test piece is set to 60 mm, and the tearing speed is set to 200 mm/min. When a tear test is conducted using a right-angle tear method in accordance with JIS K7128-3, the displacement of the first test piece in the tearing direction from the time the tear strength of the first test piece reaches a maximum until the first test piece breaks is no more than 15 mm. In the film adhesive of the present invention, it is preferred to prepare a second test piece, which is composed of a cured product of the aforementioned film adhesive having a size of 2 mm × 2 mm and a thickness of 20 μm, a copper plate having a thickness of 500 μm and disposed entirely on one side of the cured product, and a silicon wafer having a thickness of 350 μm and disposed entirely on the other side of the cured product, wherein the side surface of the cured product and the side surface of the silicon wafer are aligned with each other; With the copper plate fixed, a force is applied simultaneously at a rate of 200 μm/sec to the aligned portion of the side surface of the hardened material and the side surface of the silicon wafer in the second test piece in a direction parallel to one surface of the hardened material, until the hardened material is destroyed, or the hardened material is peeled off from the copper plate, or the hardened material is peeled off from the silicon wafer, with the maximum value of the force applied being 100 N/2 mm or greater.

The present invention provides a dicing adhesive wafer comprising a support sheet and a film-like adhesive disposed on one surface of the support sheet, wherein the film-like adhesive is the film-like adhesive of the present invention. In the dicing adhesive wafer of the present invention, the support sheet preferably consists solely of a substrate. [Effects of the Invention]

According to the present invention, a film adhesive and a dicing adhesive wafer having the film adhesive are provided. The film adhesive can be laminated with a support sheet to form a dicing adhesive wafer. Even without the need for a support sheet having an adhesive layer for direct contact with the film adhesive, the film adhesive can be prevented from remaining on the support sheet when picking up a semiconductor wafer having the film adhesive.

◇Film-like Adhesive: The film-like adhesive according to one embodiment of the present invention is a curable film-like adhesive. For a first test piece comprising a laminate of a plurality of sheets of the film-like adhesive and having a thickness of 200 μm, in accordance with JIS K7128-3, the distance between a pair of clamps holding and securing the first test piece is set to 60 mm, and the tear rate is set to 200 mm/min. When a tear test is conducted using a right-angle tear method, the displacement of the first test piece in the tear direction from the time the tear strength of the first test piece reaches a maximum until the first test piece breaks (sometimes referred to as "D ₀ " in this specification) is 15 mm or less.

The film adhesive of this embodiment can be laminated with a support sheet or dicing sheet to form a dicing adhesive wafer. Furthermore, due to its tearing properties, the film adhesive of this embodiment can prevent film adhesive residue from remaining on the support sheet or dicing sheet when picking up semiconductor wafers coated with the film adhesive, even without using a support sheet or dicing sheet with an adhesive layer for direct contact with the film adhesive. This can also prevent process failures and reduce semiconductor device manufacturing costs.

The film-like adhesive of this embodiment has curing properties, which may be either heat curing or energy ray curing, or may have both properties. In the case where the film-like adhesive has both properties, if the contribution of heat curing to the curing of the film-like adhesive is greater than that of energy ray curing, the film-like adhesive is considered to be heat curing. Conversely, if the contribution of energy ray curing to the curing of the film-like adhesive is greater than that of heat curing, the film-like adhesive is considered to be energy ray curing. For example, when the film-like adhesive is cured by heating it without irradiating it with energy rays, the film-like adhesive is considered to be heat curing.

In this specification, the term "energy ray" refers to electromagnetic waves or charged particle beams with energy quanta. Examples of energy rays include ultraviolet rays, radiation, and electron beams. Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, fusion lamp, xenon lamp, black light lamp, or LED (Light Emitting Diode) lamp as an ultraviolet ray source. Electron beams can be irradiated using electron beams generated by, for example, an electron beam accelerator. In this specification, "energy ray-hardenable" refers to the property of hardening by irradiation with energy rays, and "non-energy ray-hardenable" refers to the property of not hardening even by irradiation with energy rays.

When the aforementioned film adhesive is thermosetting, it is preferably pressure-sensitive. Film adhesives that exhibit both thermosetting and pressure-sensitive properties can adhere to various substrates by lightly pressing in their uncured state. Alternatively, film adhesives can be softened by heat and adhered to various substrates. Curing of the film adhesive ultimately results in a highly impact-resistant cured product that maintains sufficient adhesive properties even under extreme high temperature and high humidity conditions.

When the cured product of the aforementioned film adhesive is actually used, the curing conditions for forming the cured product are not particularly limited, as long as the degree of hardening of the cured product is sufficiently high. These conditions can be appropriately selected depending on the type of film adhesive. The heating temperature for heat-curing a thermosetting film adhesive is preferably 100°C to 200°C, and can be, for example, 125°C to 185°C or 150°C to 170°C. Furthermore, the heating time for heat-curing is preferably 0.5 to 5 hours, and can be, for example, 0.5 to 4 hours or 0.5 to 3 hours. The irradiance of the energy beam during energy-beam curing of an energy-beam-curable film adhesive is preferably 60 mW/ ^cm² to 320 mW/ ^cm² . Furthermore, the amount of energy beam during the energy beam curing is preferably 100 mJ/cm ² to 1000 mJ/cm ² .

[D ₀ ] The first test piece described above as the object of D ₀ measurement can be produced, for example, by using multiple sheets of film-like adhesive according to this embodiment having a thickness of less than 200 μm, laminating these sheets to produce a laminated sheet having a total thickness of 200 μm. This laminated sheet is then cut into the specified shape and dimensions, and the tear strength can be measured in accordance with JIS K7128-3. A top view of the first test piece is shown in FIG1 , along with the dimensions of the first test piece. In FIG1 , the length values for the first test piece 99 are expressed in "mm."

The thickness of the plurality of film-like adhesive sheets constituting the first test piece and the laminated sheet may be the same for all, different for all, or only partially the same. However, in order to facilitate the production of the first test piece and the laminated sheet, it is preferred that the thickness of the plurality of film-like adhesive sheets be the same for all.

The number of film adhesive sheets constituting the first test piece and the aforementioned laminated sheet is not particularly limited, as long as it is two or more sheets. The number of sheets can be arbitrarily selected based on the thickness of each film adhesive. For example, if multiple sheets of the aforementioned film adhesive have the same thickness, and if it is also considered easier to produce a single film adhesive sheet, then using ten sheets of film adhesive with a thickness of 20 μm can facilitate production of the first test piece and the aforementioned laminated sheet. However, this is merely an example, and the number of sheets and thickness of the film adhesive used are not limited to this.

The aforementioned "right-angle tear method" performed on the first specimen follows the "Plastics - Film and Sheeting - Test Methods for Tear Strength, Part 3: Right-Angled Tear Method" specified in JIS K7128-3. The distance between the clamps used to hold the first specimen in place during the tear test is 60 mm. This means that the elongated portion of the first specimen, in the tear direction, is 60 mm before the tear test begins. This length represents the length of the portion of the first specimen being tested.

During the tear test, the first specimen stretches in the tear direction. As the first specimen stretches, its tear strength increases. Furthermore, after reaching its maximum tear strength, the first specimen stretches further, causing it to break at some point. The displacement of the first specimen in the tear direction during the tear test is defined as the distance between the clamps at any point during the tear test minus the distance between the clamps at any prior point. This value is equivalent to the difference in the length of the first specimen in the tear direction at these different points in time. Furthermore, _D0 is a value obtained by subtracting the distance _Sm between the clamps when the tear strength of the first specimen reaches a maximum from the distance _Sb between the clamps when the tear strength of the first specimen reaches a maximum and then breaks ( _Sb - _Sm ).

In the film adhesive of this embodiment, D ₀ is 15 mm or less. In order to enhance the effect of suppressing the film adhesive from remaining on the support sheet, it is preferably 14.5 mm or less. For example, it can be 13 mm or less or 10 mm or less.

The lower limit of D ₀ is not particularly limited. For example, when D ₀ is 5 mm or more, the aforementioned film adhesive can be produced more easily.

D ₀ can be any numerical range defined by combining the aforementioned lower limit with any upper limit. For example, in one embodiment, D ₀ is preferably 5 mm to 15 mm, more preferably 5 mm to 14.5 mm, and can be, for example, 5 mm to 13 mm or 5 mm to 10 mm. However, these are merely examples of D ₀ .

_D0 can be adjusted by adjusting the types and amounts of the film adhesive's components. For example, D0 can be adjusted over a wide range by adjusting the types and amounts of components solid at room temperature and crosslinking agents in the film adhesive. In the case of thermosetting film adhesives, _D0 can be adjusted over a wide range by adjusting the types and amounts of the polymer component (a), the room temperature solid epoxy resin (b1), the crosslinking agent ( _f ), and other components described below.

In this manual, "normal temperature" refers to a temperature that is neither particularly cold nor particularly hot, that is, a normal temperature, for example, 15°C to 25°C.

[Adhesion Strength of Cured Film Adhesive] A semiconductor chip with a film adhesive produced using the film adhesive of this embodiment is bonded (die-bonded) to the circuit-forming surface of a substrate via the film adhesive. The film adhesive is then cured by irradiation with energy beams. Therefore, the cured film adhesive is required to exhibit sufficient adhesion to the object to which it is bonded.

The degree of the bonding force of the cured product of the film adhesive can be determined, for example, by using as an index the maximum value of the force (i.e., bonding force) obtained by preparing a second test piece (having the cured product of the film adhesive ... (The side surfaces of the cured product and the side surfaces of the silicon wafer are aligned.) With the copper plate fixed, a force is simultaneously applied at a rate of 200 μm/sec in a direction parallel to one surface of the cured product to the aligned portion of the second test piece until the cured product is destroyed, peeled from the copper plate, or peeled from the silicon wafer. In the second test piece, the cured product and the silicon wafer may have identical dimensions other than thickness, and may also have their entire side surfaces aligned. This second test piece is easily manufactured as described in the Examples below.

Figure 2 is a cross-sectional view used to schematically illustrate the aforementioned method for measuring the bonding strength of a cured film adhesive. To facilitate understanding of the features of the present invention, the following illustrations sometimes show enlarged portions of essential components for convenience. However, the dimensional ratios and other aspects of the components are not necessarily the same as in actual figures. In the figures following Figure 2, components identical to those shown in a previously described figure are designated by the same reference numerals as in the previously described figure, and detailed descriptions of these components are omitted.

During the aforementioned adhesion measurement, a second test piece 9 was prepared. The second test piece 9 comprised a cured film adhesive 90, a copper plate 91 disposed entirely on one side 90b of the cured film 90 (sometimes referred to as the "second side" in this specification), and a silicon wafer 92 disposed entirely on the other side 90a of the cured film 90 (sometimes referred to as the "first side" in this specification).

The cured film adhesive 90 is a cured film adhesive of this embodiment. The planar shapes of the first surface 90a and the second surface 90b of the cured film adhesive 90 are rectangular (square). The dimensions of the cured film adhesive 90 (the dimensions of the first surface 90a and the second surface 90b) are 2 mm x 2 mm, and the thickness of the cured film adhesive 90 is 20 μm.

The thickness of the copper plate 91 is 500 μm, and the thickness of the silicon wafer 92 is 350 μm.

In the second test piece 9, the side surface 90c of the cured film adhesive 90 is aligned with the side surface 92c of the silicon wafer 92. For example, in the cross section, the position of the side surface 90c of the film adhesive 90 is aligned with the position of the side surface 92c of the silicon wafer 92 in a direction parallel to the first surface 90a or the second surface 90b of the film adhesive 90.

Preferably, at least the portion of side surface 92c of silicon wafer 92 that aligns with side surface 90c of cured film adhesive 90 is flat. The size of the surface of silicon wafer 92 in contact with cured film 90 may be equal to or larger than the size of first surface 90a of cured film 90, or may be the same. The planar shape of the surface of silicon wafer 92 in contact with cured film 90 is preferably rectangular, but may be square, and is preferably the same as the planar shape of first surface 90a of cured film 90. As described in the embodiments below, when the cured product 90 is formed by cutting and curing a film adhesive (not shown), and the silicon wafer 92 is formed by dividing a silicon wafer (not shown), these cutting and dividing processes can be performed continuously. In this case, the contact surface between the silicon wafer 92 and the cured product 90 and the first surface 90a of the cured product 90 can be made to be the same size and shape. In addition, the side surface 90c of the cured product 90 and the side surface 92c of the silicon wafer 92 can be easily aligned.

The size of the contact surface between the copper plate 91 and the cured film adhesive 90 can be equal to or larger than the size of the second surface 90b of the cured product 90, preferably larger. The planar shape of the contact surface between the copper plate 91 and the cured product 90 is not particularly limited, as long as the copper plate 91 covers the entire second surface 90b of the cured product 90. For example, a rectangular shape is acceptable.

During the aforementioned adhesion force measurement, with copper plate 91 fixed, a force P was simultaneously applied at a rate of 200 μm/sec in a direction parallel to one surface (first surface 90a or second surface 90b) of the cured film adhesive 90 in the second test piece 9, where the cured film adhesive is aligned. This illustrates the application of force P to the alignment point using pressing mechanism 8. To achieve more accurate adhesion force measurement, the force-applying area of pressing mechanism 8 is preferably a flat surface, and pressing mechanism 8 is more preferably a flat plate. Examples of materials for pressing mechanism 8 include metals.

As described above, when force P is applied simultaneously to the cured film adhesive 90 and the silicon wafer 92 , it is preferable that the pressing mechanism 8 does not contact the copper plate 91 .

In this embodiment, the maximum value of the force P is used as the bonding force of the cured article 90. The force P is applied to the aligned portion of the side surface 90c of the cured article 90 of the film adhesive and the side surface 92c of the silicon wafer 92 until the cured article 90 is destroyed, or the cured article 90 is peeled off from the copper plate 91, or the cured article 90 is peeled off from the silicon wafer 92.

The aforementioned bonding force of the cured product of the film adhesive is preferably 100N/2mm□ or more, more preferably 110N/2mm□ or more, for example, it can be any one of 125N/2mm□ or more and 140N/2mm□ or more.

The upper limit of the bonding force is not particularly limited. For example, if the bonding force is 300 N/2 mm or less, the film adhesive can be manufactured more easily.

The aforementioned holding force can be any numerical range within a range set by arbitrarily combining any of the above lower and upper limits. For example, in one embodiment, the aforementioned holding force is preferably 100N/2mm□ to 300N/2mm□, more preferably 110N/2mm□ to 300N/2mm□, and can be, for example, 125N/2mm□ to 300N/2mm□ or 140N/2mm□ to 300N/2mm□. However, these are merely examples of the aforementioned holding force.

In this embodiment, the cured product of the film adhesive in the second test piece for adhesion is a heat-cured product obtained by heating a thermosetting film adhesive at 160°C for one hour. The cured product also includes cured products of film adhesives that have both thermosetting and energy-beam curing properties. Such cured products also include, for example, a thermosetting product obtained by irradiating a pre-thermosetting film adhesive with energy beams to obtain a semi-cured product that is not fully cured, and then heating the resulting semi-cured product at 160°C for one hour.

In this manual, the unit "N/2mm□" is synonymous with "N/(2mm×2mm)".

The aforementioned adhesive strength can be adjusted by adjusting the types and amounts of the film adhesive's components. For example, the adhesive strength can be adjusted over a wide range by adjusting the types and amounts of the polymer component, curing component, filler, and coupling agent contained in the film adhesive. In the case of a thermosetting film adhesive, the adhesive strength can be adjusted over a wide range by adjusting the types and amounts of the polymer component (a), thermosetting component (b), filler (d), and coupling agent (e), described below.

[ΔT] The film adhesive of this embodiment achieves a higher effect in suppressing film adhesive residue on the support sheet by maintaining the ΔT (N/mm) within the specified range shown below. ΔT can be calculated using the following method. Specifically, a first test piece, which is a laminate of multiple sheets of the aforementioned film-like adhesive and has a thickness of 200 μm, was subjected to a tear test using the right-angle tear method in accordance with JIS K7128-3, with the distance between a pair of clamps holding and securing the first test piece set to 60 mm and a tear rate set to 200 mm/min. The tear strength was calculated using the following formula: ΔT = (T 1 /0.6) - T _max , with the displacement of the first test piece in the tear direction when the tear strength of the first test piece reached its maximum value, T _{max ,} being D ₁ , and the tear strength when the displacement was 0.6 D ₁ being T ₁ .

The first specimen used in calculating ΔT is the same as the first specimen used in the D ₀ measurement described above. The tear test performed in calculating ΔT is the same as the tear test performed in the D ₀ measurement described above. In other words, ΔT calculation and D ₀ measurement can be performed simultaneously.

Consider the TD plane, with the tear strength T of the first specimen measured on one axis (the vertical axis) and the displacement D of the first specimen in the tear direction measured on another axis (the horizontal axis) perpendicular to the vertical axis. "T ₁ /0.6" in the above equation is the value of T when D = D ₁ , along a straight line passing through the origin (0,0) and the coordinates (0.6D ₁ , T ₁ ) in the TD plane: T = (T ₁ /0.6D ₁ ). Plot T and D for the first specimen in the TD plane to obtain a curve. When the curve has a convex shape with respect to the direction in which T increases, the following relationship holds: T ₁ /0.6 > T _max , or (T ₁ /0.6) - _{T max} > 0. Conversely, when the curve has a convex shape with respect to the direction in which T decreases, the following relationship holds: T ₁ /0.6 < _{T max} , or (T ₁ /0.6) - T _max < 0. In the film adhesive of this embodiment, in any of the aforementioned curve shapes, it is preferred that the difference between "(T ₁ /0.6)" and "T _max " be 10 N/mm or less, that is, the absolute value of ΔT (|ΔT|) be 10 N/mm or less (-10 N/mm ≦ ΔT ≦ 10 N/mm). By satisfying this condition, the effect of inhibiting film adhesive residue from remaining on the support sheet is enhanced.

In order to further enhance the above-mentioned effect, |ΔT| may be, for example, 7 N/mm or less, 5 N/mm or less, or 3 N/mm or less.

The lower limit of |ΔT| is not particularly limited. For example, when |ΔT| is 1 N/mm or more, the aforementioned film adhesive can be produced more easily.

|ΔT| can be any numerical range defined by combining the aforementioned lower limit with any upper limit. For example, in one embodiment, |ΔT| is preferably 1 N/mm to 10 N/mm or less, and can be, for example, 1 N/mm to 7 N/mm, 1 N/mm to 5 N/mm, or 1 N/mm to 3 N/mm. However, these are merely examples of |ΔT|.

|ΔT| can be adjusted by adjusting the types and amounts of the film adhesive's components. For example, |ΔT| can be adjusted over a wide range by adjusting the types and amounts of components solid at room temperature and crosslinking agents in the film adhesive. In the case of thermosetting film adhesives, |ΔT| can be adjusted over a wide range by adjusting the types and amounts of the polymer component (a), the room-temperature solid epoxy resin (b1), the crosslinking agent (f), and other components described below.

Figure 3 schematically illustrates a cross-sectional view of an example of a film-like adhesive according to this embodiment. The film-like adhesive 13 shown here comprises a first release film 151 on one surface 13a (sometimes referred to herein as the "first surface"), and a second release film 152 on the other surface 13b (sometimes referred to herein as the "second surface"), opposite to the first surface 13a. This film-like adhesive 13 is preferably stored, for example, in a roll.

The _D0 of the first test piece produced using film adhesive 13 or a film adhesive having the same composition as film adhesive 13 is preferably 15 mm or less. The |ΔT| of the first test piece produced using film adhesive 13 or a film adhesive having the same composition as film adhesive 13 is preferably 10 N/mm or less. The adhesive force of the cured product in the second test piece produced using film adhesive 13 or a film adhesive having the same composition as film adhesive 13 is preferably 100 N/2 mm or greater.

The first peeling film 151 and the second peeling film 152 can be known peeling films. The first peeling film 151 and the second peeling film 152 can be the same or different from each other, for example, in that the peeling force required for peeling from the film adhesive 13 is different.

In the film adhesive 13 shown in FIG3 , one exposed surface, resulting from the removal of the first release film 151 and the second release film 152, becomes the surface for attaching to the semiconductor wafer, while the other exposed surface becomes the surface for attaching to the substrate (bonding surface). For example, if the first surface 13a is the surface for attaching to the semiconductor wafer, the second surface 13b becomes the surface for attaching to the substrate.

FIG3 shows an example in which the release film is provided on both surfaces (the first surface 13a and the second surface 13b) of the film adhesive 13, but the release film may be provided on only one surface of the film adhesive 13, that is, only on the first surface 13a or only on the second surface 13b.

The film adhesive of this embodiment may be composed of a single layer (monolayer) or multiple layers of two or more. In the case of multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.

In addition, in this specification, the phrase "multiple layers may be the same or different from each other" is not limited to film adhesives. It means "all layers may be the same, all layers may be different, or only some layers may be the same." Furthermore, the phrase "multiple layers may be different from each other" means "at least one of the constituent material and thickness of each layer may be different from each other."

The thickness of the aforementioned film adhesive is not particularly limited, and is preferably 2μm to 100μm, more preferably 2μm to 70μm, and for example, may also be 2μm to 40μm. By having the thickness of the film adhesive be above the aforementioned lower limit, the bonding strength of the film adhesive becomes higher. When the thickness of the film adhesive is below the aforementioned upper limit, the manufacturing suitability of the film adhesive is higher, for example, the suitability when applying the adhesive composition described later to the desired thickness is higher. Here, the so-called "thickness of the film adhesive" means the thickness of the entire film adhesive, for example, the thickness of a film adhesive composed of multiple layers means the total thickness of all layers constituting the film adhesive.

The aforementioned film-like adhesive can be formed using an adhesive composition containing the constituent materials of the aforementioned film-like adhesive. For example, the adhesive composition is applied to the surface to be formed with the film-like adhesive and dried as needed to form the film-like adhesive at the target location. A thermosetting film-like adhesive can be formed using a thermosetting adhesive composition, and an energy-beam-curing film-like adhesive can be formed using an energy-beam-curing adhesive composition. The ratio of the components that do not vaporize at room temperature in the adhesive composition is generally the same as the ratio of the aforementioned components in the film-like adhesive.

The adhesive composition may be applied using a known method, for example, using the following coating machines: air knife coater, doctor blade coater, rod coater, gravure coater, roll coater, knife-roll coater, curtain coater, die coater, knife coater, screen coater, Meyer rod coater, touch coater, etc.

The drying conditions for the adhesive composition are not particularly limited. However, when the adhesive composition contains a solvent, as described below, heat drying is preferred. Adhesive compositions containing a solvent are preferably dried at, for example, 70°C to 130°C for 10 seconds to 5 minutes. The following describes film-forming adhesives and the ingredients of the adhesive composition in detail.

[Thermosetting Adhesive Composition] Examples of thermosetting adhesive compositions include a composition containing a polymer component (a) and a thermosetting component (b) (occasionally referred to as "composition (III-1)" in this specification). Each component is described below.

[Polymer Component (a)] Polymer Component (a) is a polymer compound used to impart film-forming properties and flexibility to the film-forming adhesive. Polymer Component (a) is thermoplastic and not thermosetting. In this specification, the term "polymer compound" also includes products of polycondensation reactions.

The polymer component (a) contained in the composition (III-1) and the film-like adhesive may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these polymer components (a) can be arbitrarily selected.

Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins. Among these, the polymer component (a) is preferably an acrylic resin.

The acrylic resin in polymer component (a) may be any known acrylic polymer. The weight-average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, and may be, for example, 500,000 to 1,000,000. When the weight-average molecular weight of the acrylic resin is within this range, the adhesion between the film-forming adhesive and the adherend can be easily adjusted to a preferred range. In addition, when the weight-average molecular weight of the acrylic resin is above the aforementioned lower limit, the shape stability of the film-forming adhesive (temporal stability during storage) is improved. Furthermore, when the weight average molecular weight of the acrylic resin is below the aforementioned upper limit, the film-like adhesive can easily follow the uneven surface of the adherend, thereby further suppressing the generation of voids between the adherend and the film-like adhesive.

Unless otherwise specified, the term "weight average molecular weight" in this specification refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC).

The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -45°C to 50°C, and may also be -35°C to 30°C. When the Tg of the acrylic resin is above the lower limit, the adhesion between the film adhesive and the adherend is suppressed, making it easier to remove the semiconductor chip with the film adhesive from the support sheet described below during pickup. When the Tg of the acrylic resin is below the upper limit, the adhesion between the film adhesive and the semiconductor chip is improved.

When an acrylic resin has two or more structural units, the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox equation. The Tg of the monomer from which the structural units are derived can be the value listed in polymer data manuals or adhesive manuals.

Examples of the aforementioned (meth)acrylates constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and (meth)acrylate. ) octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, (Meth)acrylates whose alkyl group is a chain structure with 1 to 18 carbon atoms, such as stearyl (meth)acrylate; (meth)acrylate cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; (meth)acrylate aralkyl esters such as benzyl (meth)acrylate; (meth)acrylate cycloalkyl esters such as dicyclopentenyl (meth)acrylate; (meth)acrylate cycloalkyl esters such as dicyclopentenyl (meth)acrylate; (meth)acrylate cycloalkyl esters such as dicyclopentenyloxyethyl (meth)acrylate; (meth)acrylate Imides; (meth)acrylates containing a glycidyl group, such as glycidyl (meth)acrylate; (meth)acrylates containing a hydroxyl group, such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (meth)acrylates containing a substituted amino group, such as N-methylaminoethyl (meth)acrylate. Here, the term "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 hydrogen atoms.

In this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid.

The acrylic resin may be, for example, a resin obtained by copolymerizing, in addition to the aforementioned (meth)acrylate, one or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxymethacrylamide.

The monomers constituting the acrylic resin may be one or two or more. In the case of two or more monomers, the combination and ratio of these monomers can be arbitrarily selected.

In addition to the aforementioned hydroxyl groups, acrylic resins may also have functional groups such as vinyl, (meth)acryl, amino, carboxyl, and isocyanate groups that can bond with other compounds. These functional groups, represented by hydroxyl groups, can bond with other compounds via a crosslinking agent (f) described below, or they can bond directly without a crosslinking agent (f). By utilizing these functional groups to bond with other compounds, the cohesive strength of the film-forming adhesive is enhanced, improving the physical stability of the film-forming adhesive.

In the present invention, a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as a "thermoplastic resin") may be used as the polymer component (a) in place of an acrylic resin, or in combination with an acrylic resin. The use of such a thermoplastic resin facilitates the removal of a semiconductor chip with a film-like adhesive from a support sheet (described later) during pickup, and the film-like adhesive can more easily follow the uneven surface of the adherend, thereby further suppressing the formation of voids between the adherend and the film-like adhesive.

The weight average molecular weight of the thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

The glass transition temperature (Tg) of the thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.

Examples of the thermoplastic resin include polyester resins, urethane resins, phenoxy resins, polybutene, polybutadiene, and polystyrene.

The composition (III-1) and the film-like adhesive may contain only one type of the aforementioned thermoplastic resin or two or more types. In the case of two or more types, the combination and ratio of these thermoplastic resins can be arbitrarily selected.

In composition (III-1), regardless of the type of polymer component (a), the ratio of the polymer component (a) content to the total content of all components other than the solvent (i.e., the ratio of the polymer component (a) content in the film-forming adhesive to the total mass of the film-forming adhesive) is preferably 5 to 40 mass%, more preferably 6 to 30 mass%, and for example, 7 to 25 mass%. The structure of the film-forming adhesive is further stabilized. By keeping the ratio below the upper limit, the balance between the effects of using the polymer component (a) and the effects of using components other than the polymer component (a) can be widely adjusted.

In composition (III-1) and the film-like adhesive, the acrylic resin content relative to the total content of polymer component (a) is preferably 25% by mass to 100% by mass, and may be, for example, 50% by mass to 100% by mass, 70% by mass to 100% by mass, or 90% by mass to 100% by mass. When the content is above the lower limit, the storage stability of the film-like adhesive is enhanced.

By adjusting the weight-average molecular weight of the polymer component (a) and the content of the polymer component (a) in the film adhesive, _D0 and |ΔT| can be more easily adjusted. For example, by using a polymer component (a) with a high weight-average molecular weight or increasing the content of the polymer component (a) with a high weight-average molecular weight in the film adhesive, _D0 and |ΔT| can be more easily reduced.

[Thermosetting Component (b)] Thermosetting component (b) is a thermosetting component used to thermally cure the film-forming adhesive. The adhesive composition and film-forming adhesive may contain a single thermosetting component (b) or two or more. When two or more thermosetting components (b) are used, the combination and ratio of these thermosetting components (b) can be arbitrarily selected.

Examples of the thermosetting component (b) include epoxy-based thermosetting resins, polyimide resins, and unsaturated polyester resins. Among these, the thermosetting component (b) is preferably an epoxy-based thermosetting resin.

Epoxy-based thermosetting resins: Epoxy-based thermosetting resins are composed of an epoxy resin (b1) and a thermosetting agent (b2). The adhesive composition and film-like adhesive may contain only one type of epoxy-based thermosetting resin or two or more types. In the case of two or more types, the combination and ratio of these epoxy-based thermosetting resins can be arbitrarily selected.

[Epoxy resin (b1)] Examples of the epoxy resin (b1) include known epoxy resins, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated product, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, phenyl skeleton epoxy resins, and other epoxy compounds having two or more functional groups.

The epoxy resin (b1) may also be an epoxy resin having an unsaturated hydrocarbon group. Epoxy resins having unsaturated hydrocarbon groups have a higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using the epoxy resin (b1) having an unsaturated hydrocarbon group, the reliability of the package obtained using the film adhesive is improved.

Examples of epoxy resins having unsaturated hydrocarbon groups include compounds having a structure in which a portion of the epoxy groups in a polyfunctional epoxy resin has been converted to groups having unsaturated hydrocarbon groups. Such compounds are obtained, for example, by reacting (meth)acrylic acid or a derivative thereof with an epoxy group.

In this specification, the term "derivative," unless otherwise specified, refers to a compound having a structure in which one or more groups of the original compound are replaced by groups other than the group (substituent). Here, "group" includes not only atomic groups composed of multiple atoms but also single atoms.

Examples of epoxy resins having unsaturated hydrocarbon groups include compounds in which an unsaturated hydrocarbon group is directly bonded to an aromatic ring or the like constituting the epoxy resin. Unsaturated hydrocarbon groups are polymerizable unsaturated groups. Specific examples of such unsaturated hydrocarbon groups include ethylene (vinyl), 2-propenyl (allyl), (meth)acryloyl, and (meth)acrylamido groups, with acryl being preferred.

The number average molecular weight of the epoxy resin (b1) is not particularly limited. From the perspective of the curability of the film adhesive and the strength and heat resistance of the cured product of the film adhesive, it is preferably 300 to 30,000, more preferably 400 to 10,000, and even more preferably 500 to 3,000. The epoxy equivalent weight of the epoxy resin (b1) is preferably 100 to 1,000 g/eq, and can be, for example, 150 to 650 g/eq, 150 to 300 g/eq, or 450 to 1,000 g/eq, or 700 to 1,000 g/eq.

By selecting an epoxy resin that is solid at room temperature as the epoxy resin (b1) and adjusting the content of the epoxy resin in the film adhesive, _D0 and |ΔT| can be more easily adjusted. For example, by increasing the content of the epoxy resin (b1) that is solid at room temperature in the film adhesive, _D0 and |ΔT| can be more easily reduced.

The epoxy resin (b1) contained in the composition (III-1) and the film adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these epoxy resins (b1) can be arbitrarily selected.

[Thermohardener (b2)] Thermohardener (b2) is a hardener for epoxy resin (b1). Examples of thermohardener (b2) include compounds having two or more functional groups reactive with epoxy groups in one molecule. Examples of these functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and groups formed by anhydriding acid groups. Phenolic hydroxyl groups, amino groups, or groups formed by anhydriding acid groups are preferred, and phenolic hydroxyl groups or amino groups are even more preferred.

Among the heat curing agents (b2), examples of phenolic curing agents having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenol, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Among the heat curing agents (b2), examples of amine-based curing agents having an amino group include dicyandiamide (DICY).

Thermosetting agent (b2) may also contain unsaturated alkyl groups. Examples of thermosetting agents (b2) containing unsaturated alkyl groups include compounds in which a portion of the hydroxyl groups of a phenolic resin are substituted with groups containing unsaturated alkyl groups, and compounds in which a group containing unsaturated alkyl groups is directly bonded to the aromatic ring of a phenolic resin. The unsaturated alkyl groups in thermosetting agent (b2) are the same as those in the aforementioned epoxy resin containing unsaturated alkyl groups.

When a phenolic curing agent is used as the thermosetting agent (b2), it is preferable that the thermosetting agent (b2) has a high softening point or glass transition temperature in order to easily adjust the adhesive strength of the film adhesive.

In the thermosetting agent (b2), the number average molecular weight of the resin component, such as a polyfunctional phenol resin, a novolac-type phenol resin, a dicyclopentadiene-type phenol resin, or an aralkyl-type phenol resin, is preferably 300 to 30,000, more preferably 400 to 10,000, and even more preferably 500 to 3,000. The molecular weight of the non-resin component, such as diphenol and dicyandiamide, in the thermosetting agent (b2) is not particularly limited, but is preferably 60 to 500, for example.

The composition (III-1) and the film adhesive may contain only one type of thermosetting agent (b2) or two or more types. In the case of two or more types, the combination and ratio of these thermosetting agents (b2) can be arbitrarily selected.

In the composition (III-1) and the film-like adhesive, the content of the thermosetting agent (b2) is preferably 1 to 60 parts by mass relative to 100 parts by mass of the epoxy resin (b1). For example, it can be any one of 1 to 35 parts by mass, 1 to 10 parts by mass, or 20 to 60 parts by mass, or 40 to 60 parts by mass. By making the content of the thermosetting agent (b2) greater than or equal to the lower limit, the film-like adhesive is easier to cure. By making the content of the thermosetting agent (b2) less than or equal to the upper limit, the moisture absorption rate of the film-like adhesive is reduced, and the reliability of the package obtained using the film-like adhesive is further improved.

In composition (III-1) and the film-like adhesive, the content of the thermosetting component (b) (e.g., the total content of the epoxy resin (b1) and the thermosetting agent (b2)) relative to 100 parts by mass of the polymer component (a) is preferably 20 to 1000 parts by mass, more preferably 20 to 700 parts by mass, and can be, for example, 50 to 500 parts by mass, 100 to 450 parts by mass, and 200 to 400 parts by mass. By having the content of the thermosetting component (b) within this range, it is easier to adjust the bonding strength between the film-like adhesive and the supporting sheet described below. Furthermore, by having the content of the thermosetting component (b) within this range, it is easier to adjust _D0 and |ΔT|.

In order to improve various physical properties of the film adhesive, composition (III-1) and the film adhesive may contain, in addition to the polymer component (a) and the thermosetting component (b), other components other than these components as needed. Examples of other components contained in composition (III-1) and the film adhesive include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), an energy ray-curable resin (g), a photopolymerization initiator (h), a colorant (i), and a general additive (j).

[Hardening accelerator (c)] Hardening accelerator (c) is a component used to adjust the hardening speed of composition (III-1) and film adhesive. Preferred curing accelerators (c) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines (phosphines in which one or more hydrogen atoms are replaced by organic groups) such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylborates such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; and inclusion compounds in which the aforementioned imidazoles serve as guest compounds.

The composition (III-1) and the film-like adhesive may contain only one type of curing accelerator (c) or two or more types. In the case of two or more types, the combination and ratio of these curing accelerators (c) can be arbitrarily selected.

When a hardening accelerator (c) is used, the content of the hardening accelerator (c) in the composition (III-1) and the film-like adhesive is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the thermosetting component (b). By ensuring that the content of the hardening accelerator (c) is at least the lower limit, the effect of using the hardening accelerator (c) can be more significantly achieved. By keeping the content of the hardening accelerator (c) below the aforementioned upper limit, the effect of suppressing the highly polar hardening accelerator (c) from migrating and segregating toward the interface between the film adhesive and the adherend under high temperature and high humidity conditions is enhanced, thereby further improving the reliability of the package obtained using the film adhesive.

[Filler (d)] By including filler (d) in a film adhesive, the film adhesive's coefficient of thermal expansion can be easily adjusted, optimizing the coefficient of thermal expansion for the object to which the film adhesive is attached. This further improves the reliability of the package created using the film adhesive. Furthermore, the inclusion of filler (d) in the film adhesive can reduce the moisture absorption rate of the cured film adhesive and improve heat dissipation.

Filler (d) can be either an organic filler or an inorganic filler, preferably an inorganic filler. Preferred inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium dioxide, red iron, silicon carbide, boron nitride, etc.; spherical beads of these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; and glass fibers. Of these, silica, alumina, or surface-modified products of these are preferred inorganic fillers.

The average particle size of the filler (d) is not particularly limited, but is preferably 10 nm to 5 μm. For example, it can be any of 10 nm to 800 nm, 10 nm to 600 nm, 20 nm to 300 nm, and 30 nm to 150 nm. By having the average particle size of the filler (d) within this range, the effects of using the filler (d) can be fully achieved, and the storage stability of the film adhesive can be further improved.

In this specification, the term "average particle size" refers to the particle size at 50% of the cumulative value ( _D50 ) in the particle size distribution curve determined by laser diffraction scattering, unless otherwise specified.

The filler (d) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. In the case of two or more types, the combination and ratio of these fillers (d) may be arbitrarily selected.

When filler (d) is used, the ratio of the filler (d) content to the total content of all components other than the solvent in composition (III-1) (i.e., the ratio of the filler (d) content in the film-like adhesive to the total mass of the film-like adhesive) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 45% by mass, and for example, 10% by mass to 20% by mass. By setting the filler (d) content within this range, the above-mentioned thermal expansion coefficient can be more easily adjusted.

[Coupling Agent (e)] The film adhesive contains a coupling agent (e) to improve its adhesion and close contact with the substrate. Furthermore, the inclusion of the coupling agent (e) in the film adhesive improves the water resistance of the cured product without compromising heat resistance. The coupling agent (e) has a functional group that reacts with an inorganic or organic compound.

The coupling agent (e) is preferably a compound having a functional group that can react with the functional groups of the polymer component (a), the thermosetting component (b), etc., and is more preferably a silane coupling agent. Preferred examples of the aforementioned silane coupling agent include: 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2- 3-(Aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-butylpropyltrimethoxysilane, 3-butylpropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, oligomeric or polymeric organosiloxanes, etc.

The coupling agent (e) contained in the composition (III-1) and the film-like adhesive may be one type or two or more types. In the case of two or more types, the combination and ratio of these coupling agents (e) may be arbitrarily selected.

When a coupling agent (e) is used, the content of the coupling agent (e) in the composition (III-1) and the film-like adhesive is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b). By ensuring that the coupling agent (e) content is above the lower limit, the following effects of using the coupling agent (e) can be more significantly achieved: improved dispersibility of the filler (d) in the resin and improved adhesion between the film-like adhesive and the adherend. By ensuring that the coupling agent (e) content is below the upper limit, outgassing can be further suppressed.

[Crosslinking Agent (f)] When using the aforementioned acrylic resins having functional groups such as vinyl, (meth)acryloyl, amino, hydroxyl, carboxyl, or isocyanate groups capable of bonding with other compounds as the polymer component (a), the composition (III-1) and the film-forming adhesive may also contain a crosslinking agent (f). This crosslinking agent (f) is used to crosslink the aforementioned functional groups by bonding with other compounds. By crosslinking with the crosslinking agent (f), the initial adhesion and cohesive strength of the film-forming adhesive can be adjusted. Furthermore, the use of the crosslinking agent (f) facilitates adjustment of _D0 and |ΔT|.

Examples of the crosslinking agent (f) include organic polyisocyanate compounds, organic polyimide compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking agents (crosslinking agents having an aziridine group).

Examples of the aforementioned organic polyisocyanate compounds include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and cycloaliphatic polyisocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyisocyanate compounds, etc."); trimers, isocyanurates, and adducts of the aforementioned aromatic polyisocyanate compounds, etc.; and isocyanate-terminated urethane prepolymers obtained by reacting the aforementioned aromatic polyisocyanate compounds, etc. with polyol compounds. The aforementioned "adducts" refer to the reaction products of the aforementioned aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, or cycloaliphatic polyisocyanate compounds with compounds containing low-molecular-weight active hydrogen, such as ethylene glycol, propylene glycol, neopentyl glycol, trihydroxymethylpropane, or castor oil. Examples of the adducts include the toluene diisocyanate trimer adduct of trihydroxymethylpropane described below. Furthermore, the term "isocyanate-terminated urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the terminal end of the molecule.

More specifically, the organic polyisocyanate compounds include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-phenylenediisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate. diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; compounds formed by adding one or more of toluene diisocyanate, hexamethylene diisocyanate, and xylylenediisocyanate to all or part of the hydroxyl groups of a polyol such as trihydroxymethylpropane; lysine diisocyanate, etc.

Examples of the organic polyimide compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trihydroxymethylpropane-tris-β-aziridine propionate, tetrahydroxymethylmethane-tris-β-aziridine propionate, and N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylene melamine.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), a hydroxyl-containing polymer is preferably used as the polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, a crosslinked structure can be easily introduced into the film-like adhesive through the reaction between the crosslinking agent (f) and the polymer component (a).

The composition (III-1) and the film-like adhesive may contain only one crosslinking agent (f) or two or more crosslinking agents (f). In the case of two or more crosslinking agents (f), the combination and ratio of these crosslinking agents (f) can be arbitrarily selected.

When a crosslinking agent (f) is used, the content of the crosslinking agent (f) in the adhesive composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the polymer component (a). By having the crosslinking agent (f) content be greater than the lower limit, the effect of using the crosslinking agent (f) can be more significantly achieved. By having the crosslinking agent (f) content be less than the upper limit, excessive use of the crosslinking agent (f) can be suppressed. In addition, by having the crosslinking agent (f) content be within this range, _D0 and |ΔT| can be more easily adjusted. For example, by increasing the aforementioned content of the crosslinking agent (f), D ₀ and |ΔT| can be more easily reduced.

When no crosslinking agent (f) is used, that is, when the content of the crosslinking agent (f) is 0 parts by mass, there is no need to set a time from the formation of the film-like adhesive until the completion of the crosslinking reaction by the crosslinking agent (f), which is advantageous in that the step time can be shortened.

[Energy ray curing resin (g)] The film adhesive contains an energy ray curing resin (g), which allows its properties to be changed by irradiation with energy rays.

The energy ray-curable resin (g) is obtained from an energy ray-curable compound. Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, preferably acrylate compounds having a (meth)acryloyl group.

Examples of the acrylate compounds include trihydroxymethylpropane tri(meth)acrylate, tetrahydroxymethylmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. (Meth)acrylates containing a chain aliphatic skeleton such as acrylates; (meth)acrylates containing a cyclic aliphatic skeleton such as dicyclopentyl di(meth)acrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylates; urethane (meth)acrylate oligomers; epoxy-modified (meth)acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; itaconic acid oligomers, etc.

The weight average molecular weight of the energy ray-curable resin (g) is preferably 100 to 30,000, more preferably 300 to 10,000.

The energy ray curable resin (g) contained in the composition (III-1) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio of these energy ray curable resins (g) can be arbitrarily selected.

When the energy ray-curable resin (g) is used, the content of the energy ray-curable resin (g) in the composition (III-1) is preferably 1% by mass to 95% by mass, for example, 1% by mass to 50% by mass, 1% by mass to 25% by mass, and 1% by mass to 10% by mass.

[Photopolymerization initiator (h)] When the composition (III-1) and the film-like adhesive contain the energy ray-curable resin (g), a photopolymerization initiator (h) may be contained in order to efficiently carry out the polymerization reaction of the energy ray-curable resin (g).

Examples of the photopolymerization initiator (h) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoic acid methyl ester, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 2,2-dimethoxy-1,2-diphenylethane-1-one; acyl oxides such as bis(2,4,6-trimethylbenzyl)phenylphosphine oxide and 2,4,6-trimethylbenzyldiphenylphosphine oxide; Phosphine compounds; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketoalcohol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thiothione compounds such as thiothione; peroxide compounds; diketone compounds such as diacetyl; benzoyl; dibenzoyl; benzophenone; 2,4-diethylthiothione; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone, etc. In addition, as the photopolymerization initiator (h), for example, photosensitizers such as amine may also be used.

The composition (III-1) and the film-like adhesive may contain only one photopolymerization initiator (h) or two or more types. When there are two or more types, the combination and ratio of these photopolymerization initiators (h) can be arbitrarily selected.

When a photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the composition (III-1) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 5 parts by mass, based on 100 parts by mass of the energy ray-curable resin (g).

[Colorant (i)] Colorant (i) is a component in film adhesives and their cured products that adjusts the transmittance of light of various wavelengths. Examples of colorant (i) include well-known colorants such as inorganic pigments, organic pigments, and organic dyes.

Examples of the organic pigments and organic dyes include ammonium pigments, cyanine pigments, merocyanine pigments, croconium pigments, squalilium pigments, azulenium pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphtholactam pigments, azo pigments, condensed azo pigments, indigo pigments, perinone pigments, and perylene pigments. , dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, thioindigo pigments, metal complex pigments (metal complex dyes), dithiol metal complex pigments, indoxyl pigments, triallyl methane pigments, anthraquinone pigments, dioxazine pigments, naphthol pigments, methine azo pigments, benzimidazolone pigments, pyranthrone pigments and threne pigments, etc.

Examples of the inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (Indium Tin Oxide)-based pigments, and ATO (Antimony Tin Oxide)-based pigments.

The coloring agent (i) contained in the composition (III-1) and the film adhesive may be only one type or two or more types. In the case of two or more types, the combination and ratio of these coloring agents (i) can be arbitrarily selected.

When a colorant (i) is used, the content of the colorant (i) in the composition (III-1) and the film-forming adhesive can be appropriately adjusted, for example, depending on the type of colorant (i). Generally, regardless of the type of colorant (i) in the composition (III-1), the ratio of the colorant (i) content to the total content of all components other than the solvent (i.e., the ratio of the colorant (i) content in the film-forming adhesive to the total mass of the film-forming adhesive) is preferably 0.01% by mass to 10% by mass. When the ratio is above the lower limit, the effect of using the colorant (i) can be more significantly achieved. When the ratio is below the upper limit, excessive use of the colorant (i) can be suppressed.

[General Additive (j)] General additives (j) can be any known additives and can be selected according to the intended purpose without particular limitation. Preferred general additives (j) include, for example, plasticizers, antistatic agents, antioxidants, gettering agents, defoaming agents, and leveling agents.

The general-purpose additive (i) contained in the composition (III-1) and the film-like adhesive may be a single type or two or more types. In the case of two or more types, the combination and ratio of these general-purpose additives (i) can be arbitrarily selected. The content of the general-purpose additive (i) in the composition (III-1) and the film-like adhesive is not particularly limited and can be appropriately selected depending on the type of general-purpose additive (i).

[Solvent] Composition (III-1) preferably further contains a solvent. Composition (III-1) containing a solvent improves handling properties. The solvent is not particularly limited. Preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. Composition (III-1) may contain only one solvent or two or more. In the case of two or more solvents, the combination and ratio of these solvents can be arbitrarily selected.

From the viewpoint of being able to more uniformly mix the components in the composition (III-1), the solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like.

The content of the solvent in the composition (III-1) is not particularly limited and may be appropriately selected depending on the types of components other than the solvent.

[Energy ray-curable adhesive composition] Examples of energy ray-curable adhesive compositions include compositions containing energy ray-curable components (sometimes referred to as "composition (III-2)" in this specification), and compositions containing energy ray-curable components, polymers without energy ray-curable groups, and photopolymerization initiators.

Examples of the energy ray-curable component include resins having energy ray-polymerizable unsaturated groups (energy ray-polymerizable groups) such as acryl groups, and groups reactive with other compounds such as glycidyl groups. The epoxy resin (b1) in the composition (III-1) described above contains an epoxy resin corresponding to the energy ray-curable component.

Examples of the aforementioned polymer lacking energy ray-curable groups include acrylic resins, phenoxy resins, urethane resins, polyester resins, rubber-based resins, and acrylic urethane resins. Of these, acrylic resins are preferred. The polymer component (a) in (III-1) described above contains a component corresponding to the aforementioned polymer lacking energy ray-curable groups.

Examples of the photopolymerization initiator include the same photopolymerization initiators as those mentioned above as the photopolymerization initiator (h) in the composition (III-1).

The contents of the energy ray-curable component, the polymer without an energy ray-curable group, and the photopolymerization initiator in composition (III-2) can be appropriately adjusted depending on the types of these components and are not particularly limited. For example, if any of the energy ray-curable component, the polymer without an energy ray-curable group, and the photopolymerization initiator contains a component equivalent to any component contained in composition (III-1), the content of that component in composition (III-2) can be set to the same as the content of the corresponding component in composition (III-1).

Composition (III-2) may also contain other components other than the aforementioned energy ray-curable component, the aforementioned polymer without an energy ray-curable group, and the aforementioned photopolymerization initiator, depending on the intended purpose. Examples of such other components include one or more selected from the group consisting of epoxy resins, thermosetting agents, fillers, coupling agents, crosslinking agents, colorants, general-purpose additives, and solvents.

The epoxy resin, thermosetting agent, filler, coupling agent, crosslinking agent, colorant, general additive, and solvent in composition (III-2) may be the same as the epoxy resin (b1), thermosetting agent (b2), filler (d), coupling agent (e), crosslinking agent (f), colorant (i), general additive (j), and solvent in composition (III-1).

The contents of the epoxy resin, thermosetting agent, filler, coupling agent, crosslinking agent, coloring agent, general additive, and solvent in the composition (III-2) can be appropriately adjusted according to the purpose and are not particularly limited.

As another example of a preferable curable film adhesive of the present embodiment, the following film adhesive can be cited: a curable film adhesive, wherein the film adhesive contains a polymer component, a thermosetting component, a curing accelerator, and a coupling agent, wherein the polymer component includes an acrylic resin, the thermosetting component includes an epoxy-based thermosetting resin, the epoxy-based thermosetting resin is composed of an epoxy resin and a thermosetting agent, the polymer component in the film adhesive has a content ratio of 5% to 40% by mass relative to the total mass of the film adhesive, the acrylic resin in the film adhesive has a content ratio of 25% to 100% by mass relative to the total mass of the polymer component, and the coupling agent in the film adhesive has a content ratio of 10% to 20%. The ratio of the thermosetting component content is 20 parts by mass to 100 parts by mass of the polymer component content, and the content of the thermosetting agent in the film-like adhesive is 1 part by mass to 60 parts by mass relative to 100 parts by mass of the epoxy resin content. For a first test piece comprising a laminate of multiple sheets of the film-like adhesive and having a thickness of 200 μm, in accordance with JIS K7128-3, the distance between a pair of clamps holding and securing the first test piece is set to 60 mm, and the tearing speed is set to 200 mm/min. When a tear test is conducted using a right-angle tear method, the displacement of the first test piece in the tear direction from the time the tear strength of the first test piece reaches a maximum until the first test piece breaks is no more than 15 mm.

[Method for Producing Adhesive Compositions] Adhesive compositions (thermosetting adhesive compositions, energy beam-curing adhesive compositions) can be obtained by blending the components that constitute the adhesive composition. The order of adding the components is not particularly limited, and two or more components may be added simultaneously. When using a solvent, the solvent can be mixed with any component other than the solvent and the resulting mixture can be diluted before use, or the solvent and the resulting mixture can be mixed without diluting any of the components other than the solvent.

The method for mixing the ingredients during preparation is not particularly limited and can be appropriately selected from the following known methods: mixing by rotating a stirrer or impeller, mixing using a mixer, mixing by applying ultrasonic waves, etc. The temperature and time for adding and mixing the ingredients are not particularly limited as long as they do not degrade the ingredients and can be adjusted appropriately; the temperature is preferably between 15°C and 30°C.

◇ Dicing Adhesive Wafer: One embodiment of the dicing adhesive wafer of the present invention comprises a support sheet and a film adhesive disposed on one surface of the support sheet. The film adhesive is the film adhesive of the embodiment of the present invention described above. This dicing adhesive wafer of this embodiment can be used, for example, to separate semiconductor wafers into semiconductor chips by dicing, thereby producing sheets of semiconductor chips with film adhesive as described above. In other words, the support sheet in the dicing adhesive wafer can function as a dicing sheet.

[Support Sheet] The support sheet may be composed of a single layer or multiple layers. When the support sheet is composed of multiple layers, the materials and thicknesses of the multiple layers may be the same or different. The combination of these layers is not particularly limited as long as it does not impair the effects of the present invention.

Examples of the aforementioned support sheet include: a support sheet consisting solely of a substrate; a support sheet comprising a substrate and an adhesive layer disposed on one surface of the substrate; a support sheet comprising a substrate and a functional layer other than the adhesive layer disposed on one surface of the substrate, and the like.

When the supporting sheet comprises the aforementioned substrate and adhesive layer, in the aforementioned dicing adhesive sheet, the adhesive layer is disposed between the substrate and the aforementioned film-like adhesive.

When the support sheet has the aforementioned substrate and functional layer, the functional layer can be arranged on the film adhesive side of the substrate or on the side of the substrate opposite to the film adhesive side. In this embodiment, the functional layer arranged on the film adhesive side of the substrate is referred to as the "middle layer," and the functional layer arranged on the side of the substrate opposite to the film adhesive side is referred to as the "back layer." By arranging the aforementioned middle layer on the film adhesive side of the substrate, a new function other than adhesion is imparted to the support sheet or the dicing adhesive. By arranging the aforementioned back layer on the side of the substrate opposite to the film adhesive side, a new function other than adhesion is imparted to the support sheet or the dicing adhesive. Examples of the back layer include: an antistatic layer for preventing the support sheet or dicing adhesive wafer from being charged; an anti-adhesion layer for preventing the support sheets or dicing adhesive wafers from adhering to each other when the support sheets or dicing adhesive wafers are stacked and stored, or preventing the support sheets or dicing adhesive wafers from adhering to the adsorption platform, etc.

The aforementioned support sheet, composed solely of a substrate, is suitable not only for use as a dicing sheet but also as a carrier sheet. A dicing wafer having such a support sheet composed solely of a substrate is used by attaching the surface of the film adhesive opposite to the side having the support sheet (i.e., the substrate) (i.e., the aforementioned first surface) to one side of a semiconductor wafer. Using a support sheet composed solely of a substrate allows for low-cost production of the dicing wafer.

The aforementioned support sheet comprising a base material and an adhesive layer, and the aforementioned support sheet comprising a base material and a functional layer, are suitable for use as dicing sheets. Dicing wafers comprising such support sheets are also used by attaching the surface (first surface) of the film adhesive opposite to the side comprising the support sheet to one side of a semiconductor wafer. When using a support sheet comprising a base material and an adhesive layer, the adhesion or close contact between the support sheet and the film adhesive in the dicing wafer can be easily adjusted. When using a support sheet comprising a base material and a functional layer, the support sheet or dicing wafer exhibits functions other than adhesiveness corresponding to the characteristics of the functional layer.

Because the dicing wafer of this embodiment includes the aforementioned film adhesive, even when the support sheet does not have an adhesive layer in direct contact with the film adhesive, film adhesive residue can be suppressed when semiconductor chips with the film adhesive are produced and picked up using the dicing wafer. Specifically, the effects of the present invention are most significantly exhibited when using dicing wafers with a structure where the adhesive layer and the film adhesive are not in direct contact, such as dicing wafers with a film adhesive applied to a support sheet consisting solely of a substrate, or dicing wafers with a substrate and the aforementioned functional layer.

However, the dicing adhesive wafer of this embodiment may also have an adhesive layer that is in direct contact with the film adhesive. In this case, the film adhesive and the adhesive layer can more easily prevent the film adhesive from remaining on the support sheet when picking up the semiconductor wafer with the film adhesive.

The use of the die-bonding sheet will be explained in detail later. Below, we will explain the various layers that make up the support sheet.

[Substrate] The aforementioned substrate is in the form of a sheet or film. Examples of the constituent material of the aforementioned substrate include various resins. Examples of the aforementioned resin include polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE); polyolefins other than polyethylenes such as polypropylene, polybutene, polybutadiene, polymethylpentene, and norbornene resins; ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylate copolymers, and ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride resins (resins obtained using vinyl chloride as a monomer) such as polyvinyl chloride and vinyl chloride copolymers; and polystyrene. Ethylene; polycycloolefins; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polyethylene butylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, and wholly aromatic polyesters containing aromatic cyclic groups in all constituent units; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylates; polyurethanes; polyacrylic urethanes; polyimides; polyamides; polycarbonates; fluororesins; polyacetals; modified polyphenylene ethers; polyphenylene sulfides; polysulfones; and polyetherketones. Also, examples of the aforementioned resins include polymer alloys such as mixtures of the aforementioned polyesters and resins other than polyesters. In polymer alloys of the aforementioned polyesters and resins other than polyesters, the amount of the resin other than polyester is preferably relatively small. Examples of the resin include crosslinked resins obtained by crosslinking one or more of the resins listed above; and modified resins such as ionomers obtained by crosslinking one or more of the resins listed above.

Among these, the aforementioned resins as the substrate material are preferably olefinic resins containing olefin-derived units, such as polyethylene, polyolefins other than polyethylene, and ethylene copolymers. In dicing adhesive sheets constructed with the aforementioned film adhesive directly contacting the substrate, dicing adhesive sheets containing such resins on the substrate's contact surface with the film adhesive exhibit a higher effectiveness in suppressing film adhesive residue on the support sheet (in other words, the substrate). Furthermore, the aforementioned resins as the substrate material are preferably free of polar groups such as carboxyl, carbonyl, or hydroxyl groups. A dicing wafer in which the surface of the substrate that contacts the film adhesive contains this resin also has a higher effect of suppressing the film adhesive from remaining on the support sheet (in other words, the substrate).

The resin constituting the substrate may be only one type or two or more types. In the case of two or more types, the combination and ratio of these resins can be arbitrarily selected.

The substrate may be composed of a single layer (single layer) or a plurality of layers including two or more layers. In the case of a plurality of layers, the layers may be the same or different from each other, and the combination of the layers is not particularly limited.

The substrate thickness is preferably 50 μm to 300 μm, more preferably 60 μm to 150 μm. A substrate thickness within this range further improves the flexibility of the die-bonding wafer and its adhesion to the semiconductor wafer. Here, "substrate thickness" refers to the thickness of the entire substrate. For example, for a multi-layer substrate, the thickness refers to the combined thickness of all layers comprising the substrate.

In addition to the aforementioned resin and other main components, the substrate may also contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), etc.

The substrate can be transparent or opaque, can be colored according to the purpose, and can also be vapor-deposited with other layers.

To improve adhesion between the substrate and layers disposed thereon (e.g., adhesive layers, film adhesives, etc.), the surface may be subjected to surface roughening treatments such as sandblasting or solvent treatment; or oxidation treatments such as coma discharge treatment, electron beam irradiation, plasma treatment, ozone/UV irradiation, flame treatment, chromic acid treatment, and hot air treatment. Furthermore, the substrate surface may be primed. Also, the substrate surface may have a release layer. This release layer can be formed by applying a release treatment to the substrate surface using various known release agents. Alternatively, the substrate may be made adhesive on at least one side by containing a specific range of components (e.g., resins).

In cases where the support sheet is composed only of a substrate or has an exposed surface of the substrate, and the outermost layer of the film adhesive side of the support sheet is the substrate, in order to further improve the effect of suppressing the film adhesive residue on the support sheet (in other words, the substrate) when picking up a semiconductor chip with a film adhesive, it is preferred that the surface of the film adhesive side of the substrate (sometimes referred to as the "first surface" in this specification) is not subjected to the aforementioned oxidation treatment, the aforementioned primer treatment, or other surface treatments.

The substrate can be manufactured using a known method. For example, a substrate containing a resin can be manufactured by molding a resin composition containing the aforementioned resin.

[Adhesive Layer] The adhesive layer is in sheet or film form and contains an adhesive. Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ether, polycarbonate, and polyester resins.

In this specification, "adhesive resin" includes both adhesive resins and adhesive resins. For example, the aforementioned adhesive resins include not only resins that have adhesive properties themselves, but also resins that exhibit adhesive properties by combining with other ingredients such as additives, and resins that exhibit adhesive properties when triggered by heat or water.

The adhesive layer may be composed of a single layer or a plurality of layers. In the case of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.

The thickness of the adhesive layer is not particularly limited, but is preferably 1 μm to 100 μm, and can be, for example, 1 μm to 60 μm or 1 μm to 30 μm. Herein, the term "thickness of the adhesive layer" refers to the thickness of the adhesive layer as a whole. For example, the term "thickness of a multi-layered adhesive layer" refers to the combined thickness of all layers comprising the adhesive layer.

The adhesive layer can be formed using either an energy-beam-curable adhesive or a non-energy-beam-curable adhesive. In other words, the adhesive layer can be either energy-beam-curable or non-energy-beam-curable. Energy-beam-curable adhesive layers can easily adjust their physical properties before and after curing.

The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition is applied to the surface to be formed and dried as needed to form the adhesive layer at the target location. The ratio of the components in the adhesive composition that do not vaporize at room temperature is generally the same as the ratio of the components in the adhesive layer.

The adhesive composition can be applied in the same manner as the adhesive composition described above.

When the adhesive layer is energy-ray-curable, examples of the energy-ray-curable adhesive composition include the following: an adhesive composition (I-1) containing a non-energy-ray-curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-1a)") and an energy-ray-curable compound; an adhesive composition (I-2) containing an energy-ray-curable adhesive resin (I-2a) having an unsaturated group introduced into the side chain of the adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-2a)"); and an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy-ray-curable compound.

When the adhesive layer is non-energy ray-curable, examples of the non-energy ray-curable adhesive composition include the adhesive composition (I-4) containing the aforementioned adhesive resin (I-1a).

Adhesive compositions (I-1) to (I-4) can be produced by the same method as the adhesive composition described above, except that the ingredients are different.

[Functional Layer] The functional layer is preferably in sheet or film form and contains a resin. The functional layer may be composed solely of a resin or may contain a resin and components other than resins. A functional layer containing a resin can be formed, for example, by molding the resin or a functional layer-forming composition containing the resin. Alternatively, the functional layer can be formed by applying the functional layer-forming composition to the surface on which the functional layer is to be formed and drying it as needed.

The content of the resin in the functional layer-forming composition is not particularly limited and can be, for example, 10% by mass to 90% by mass, but this is merely an example.

The functional layer may be composed of a single layer (single layer) or a plurality of layers. In the case of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the functional layers is not particularly limited.

The thickness of the functional layer is not particularly limited and can be appropriately set depending on the type of functional layer. Herein, the term "thickness of the functional layer" refers to the thickness of the entire functional layer. For example, the term "thickness of a multi-layered functional layer" refers to the combined thickness of all layers comprising the functional layer.

Next, an example of cutting a bonded wafer according to this embodiment will be described with reference to the drawings.

Figure 4 is a schematic cross-sectional view of an example of a dicing adhesive wafer according to this embodiment. The dicing adhesive wafer 101 shown here includes a support sheet 10, with a film-like adhesive 13 applied to one side (first side) 10a of the support sheet 10. The support sheet 10 is composed solely of a substrate 11. In other words, the dicing adhesive wafer 101 has a structure in which the film-like adhesive 13 is deposited on one side (sometimes referred to as the "first side" in this specification) 11a of the substrate 11. Furthermore, the dicing adhesive wafer 101 further includes a release film 15 applied to the film-like adhesive 13.

In the wafer bonding chip 101, a film adhesive 13 is deposited on the first surface 11a of the substrate 11. A jig adhesive layer 16 is deposited on a portion of the surface 13a of the film adhesive 13 opposite to the side having the substrate 11 (sometimes referred to as the "first surface" in this specification), i.e., an area near the periphery. A release film 15 is deposited on the surface of the first surface 13a of the film adhesive 13 not deposited with the jig adhesive layer 16 and on the surface 16a of the jig adhesive layer 16 not in contact with the film adhesive 13 (the top surface and side surfaces). The first surface 11 a of the base material 11 is identical to the first surface 10 a of the supporting sheet 10 .

The film adhesive 13 is as described above. The release film 15 is the same as the first release film 151 or the second release film 152 shown in FIG3 .

The jig adhesive layer 16 may be, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which layers containing an adhesive component are laminated on both sides of a sheet serving as a core material.

The die-cutting bond sheet 101 is used by attaching the inner surface of a semiconductor wafer (not shown) to the first surface 13a of the film adhesive 13 with the peeling film 15 removed, and then attaching the upper surface of the surface 16a of the jig adhesive layer 16 to a jig such as a ring frame.

Figure 5 schematically illustrates a cross-sectional view of another example of a dicing wafer according to this embodiment. Die-cutting wafer 102 shown here is identical to die-cutting wafer 101 shown in Figure 4 , except that it lacks the jig adhesive layer 16 . Specifically, die-cutting wafer 102 has a film adhesive 13 deposited on the first surface 11a of substrate 11 (first surface 10a of support sheet 10), and a release film 15 deposited across the entire first surface 13a of film adhesive 13. In other words, die-cutting wafer 102 is constructed by depositing substrate 11, film adhesive 13, and release film 15 in this order throughout the thickness direction.

The dicing adhesive chip 102 shown in FIG5 is in a state where the peeling film 15 is removed and a portion of the center side of the film adhesive 13 in the width direction of the film adhesive 13 is attached to the inner surface of a semiconductor wafer (not shown). The area near the periphery of the film adhesive 13 is then attached to a jig such as a ring frame for use.

The die-cutting adhesive sheet of this embodiment is not limited to the die-cutting adhesive sheet shown in Figures 4 and 5. Within the scope of not impairing the effect of the present invention, part of the structure of the die-cutting adhesive sheet shown in Figures 4 and 5 can be changed or deleted, or other structures can be added to the die-cutting adhesive sheet described above.

For example, the dicing adhesive wafer shown in Figures 4 and 5 can have other layers that are not equivalent to any of the substrate, film-like adhesive, and peeling film arranged at any position. Examples of the aforementioned other layers include the adhesive layer and functional layers (middle layer, back layer) described above. The adhesive layer is arranged between the substrate 11 and the film-like adhesive 13. The middle layer among the functional layers is also arranged between the substrate 11 and the film-like adhesive 13. The back layer among the functional layers is arranged on the surface of the substrate 11 opposite to the first surface 11a, and can also be the outermost layer in the dicing adhesive wafer.

In the dicing adhesive wafer shown in Figures 4 and 5, a gap can also be generated between the release film and the layer directly contacting the release film. In the dicing adhesive wafer shown in Figures 4 and 5, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

◇Method for Manufacturing Dicing Bonded Chips The aforementioned dicing bonded chips can be manufactured by stacking the aforementioned layers in a corresponding positional relationship and adjusting the shapes of some or all of the layers as needed. The formation methods of the various layers are as described above.

For example, when manufacturing a support sheet, when depositing an adhesive layer on a substrate, simply apply the aforementioned adhesive composition to the substrate and allow it to dry as needed. Alternatively, the adhesive layer can be deposited on the substrate by applying the adhesive composition to a release film, allowing it to dry as needed, thereby pre-forming an adhesive layer on the release film. The exposed surface of the adhesive layer is then bonded to one side of the substrate. In this case, the adhesive composition is preferably applied to the release-treated surface of the release film. While the example above illustrates the case of depositing an adhesive layer on a substrate, the above method can also be applied to depositing other layers, such as the functional layer described above, on a substrate, or depositing the aforementioned film-like adhesive on a substrate. When depositing the aforementioned film-like adhesive, the aforementioned adhesive composition is used.

On the other hand, for example, when a new layer (hereinafter referred to as the "second layer") is deposited on the topmost layer already deposited on a substrate (hereinafter referred to as the "first layer"), the second layer is pre-formed on a release film using a composition for forming the second layer. The exposed surface of the formed second layer, opposite to the side in contact with the release film, is bonded to the exposed surface of the first layer on the substrate, thereby forming a continuous two-layered structure (in other words, a layered structure of the first and second layers). In this case, the composition is preferably applied to the release-treated surface of the release film. After the laminate structure is formed, the release film can be removed as needed. In the case where the second layer is the film-like adhesive, the adhesive composition is used as the composition for forming the second layer.

In this way, since all layers other than the substrate constituting the dicing adhesive wafer can be pre-formed on a release film and then laminated on the surface of the target layer, the dicing adhesive wafer can be manufactured by appropriately selecting the layer using this step as needed.

Furthermore, the dicing adhesive wafer is usually stored with a peeling film attached to the surface of the outermost layer (e.g., film adhesive) on the side opposite to the support sheet in the dicing adhesive wafer. Therefore, a dicing adhesive wafer with a release film can be obtained by applying the aforementioned adhesive composition or the like to form a composition constituting the outermost layer on the release film (preferably the release-treated surface of the release film), drying the adhesive composition as needed, thereby pre-forming the outermost layer on the release film. The remaining layers are then applied to the exposed surface of the layer opposite to the side in contact with the release film using any of the aforementioned methods, without removing the release film to maintain the bonded state.

◇Method for manufacturing semiconductor devices (method for using a dicing wafer) [Manufacturing method (1)] The dicing wafer of one embodiment of the present invention described above can be used when manufacturing semiconductor devices. As a method for manufacturing a semiconductor device in this case, for example, the following manufacturing method (sometimes referred to as "manufacturing method (1)" in this specification) can be cited, which comprises: a lamination step (1), in which a laminate (1) is manufactured using the aforementioned dicing adhesive chip, wherein the aforementioned laminate (1) has a semiconductor wafer, and the aforementioned dicing adhesive chip is attached to the inner surface of the aforementioned semiconductor wafer by the aforementioned film adhesive in the aforementioned dicing adhesive chip; a division/cutting step, in which the aforementioned semiconductor wafer in the aforementioned laminate (1) is divided to manufacture semiconductor chips, and the aforementioned film adhesive is cut along the division portion of the aforementioned semiconductor wafer to manufacture a semiconductor chip assembly (1) having a film adhesive, wherein the aforementioned The semiconductor chip assembly (1) with a film adhesive is composed of a plurality of semiconductor chips with a film adhesive formed by the aforementioned semiconductor chip and the aforementioned film adhesive provided on the inner surface of the aforementioned semiconductor chip after cutting, which are held on the aforementioned support sheet; the picking up (1) step is to pull the semiconductor chip with a film adhesive in the aforementioned semiconductor chip assembly (1) away from the aforementioned support sheet and pick it up, thereby obtaining the semiconductor chip with a film adhesive; and the die bonding step is to bond the obtained semiconductor chip in the aforementioned semiconductor chip with a film adhesive to the circuit forming surface of the substrate by means of the film adhesive in the aforementioned semiconductor chip with a film adhesive. In the manufacturing method (1), a semiconductor device can be manufactured by the same method as the previous method except that the dicing wafer of one embodiment of the present invention is used instead of the previous dicing wafer.

[Lamination (1) step] In the aforementioned lamination (1) step, for example, the surface of the aforementioned film adhesive in the aforementioned dicing adhesive sheet that is opposite to the aforementioned support sheet side (i.e., the first surface) is attached to the inner surface of the semiconductor wafer, thereby producing a laminate (1). This step can be performed using the same method as the previous method of attaching the dicing adhesive sheet to the inner surface of the semiconductor wafer, except that the dicing adhesive sheet of one embodiment of the present invention is used instead of the previous dicing adhesive sheet.

[Split/cut step] In the aforementioned split/cut step, the order of splitting the semiconductor wafer in the laminate (1) (manufacturing of semiconductor chips) and cutting the film adhesive in the laminate (1) is not particularly limited. The steps may be performed in the order of splitting the semiconductor wafer and cutting the film adhesive, or in the order of cutting the film adhesive and splitting the semiconductor wafer. The splitting of the semiconductor wafer and the cutting of the film adhesive may also be performed simultaneously. In addition, when the semiconductor wafer division and the adhesive film cutting are not performed simultaneously, the semiconductor wafer division and the adhesive film cutting can be performed continuously or in stages.

Semiconductor wafer separation and film adhesive cutting can be performed using known methods. For example, semiconductor wafer separation and film adhesive cutting can be performed continuously using blade dicing, laser dicing using laser irradiation, or water dicing using a spray of water containing an abrasive. However, this is only one example of a method for semiconductor wafer separation and film adhesive cutting.

The film adhesive is cut along the semiconductor wafer's dividing portion. However, in this case, when the film adhesive is cut after the semiconductor wafer is divided, the film adhesive is cut along the semiconductor wafer's dividing portion, that is, the periphery of the semiconductor chip. On the other hand, when the film adhesive is cut before the semiconductor wafer is divided, or when the film adhesive is cut simultaneously with the semiconductor wafer's division, the film adhesive is cut along the portion of the semiconductor wafer intended for division.

The semiconductor chip assembly (1) with film adhesive produced in this step is a plurality of semiconductor chips with film adhesive held (fixed) in an orderly arranged state on the aforementioned supporting sheet that originally constitutes the aforementioned dicing and bonding chip.

[Pick-up (1) step] In the aforementioned pick-up (1) step, the semiconductor chip with a film adhesive in the semiconductor chip assembly (1) with a film adhesive can be pulled off the support sheet and picked up using a known method. In this step, by using the film adhesive (dicing adhesive chip) of one embodiment of the present invention, even if the support sheet does not have an adhesive layer for direct contact with the film adhesive, it is possible to suppress the film adhesive from remaining on the support sheet when picking up the semiconductor chip with a film adhesive.

[Die Bonding Step] In the aforementioned die bonding step, the picked-up semiconductor chip with the film adhesive can be bonded to the circuit formation surface of the substrate using the film adhesive therein by a known method.

After the aforementioned die-bonding step, semiconductor packages and semiconductor devices can be manufactured using the same methods as previously described. For example, wire bonding can be performed after stacking one or more semiconductor chips on the die-bonded semiconductor chip as needed. The film adhesive is then thermally cured, and the resulting cured product is sealed with a resin. By completing these steps, a semiconductor package is produced. This semiconductor package can then be used to manufacture the desired semiconductor device.

FIG6 is a cross-sectional view for schematically illustrating the manufacturing method (1). Here, the manufacturing method (1) is shown when the dicing and bonding wafer 101 shown in FIG4 is used.

FIG6A shows a laminate (1) 119A obtained in the lamination (1) step. The laminate (1) 119A comprises a semiconductor wafer 9 and a dicing adhesive chip 101 disposed on the inner surface 9b of the semiconductor wafer 9. FIG6B shows a semiconductor chip assembly (1) 119B with a film adhesive obtained in the segmentation/cutting step. The semiconductor chip assembly (1) 119B with a film adhesive is composed of a plurality of semiconductor chips 139' with a film adhesive formed by a semiconductor chip 9' and a film adhesive 130 disposed on the inner surface 9b' of the semiconductor chip 9' after cutting, and held on a support sheet 10. FIG6C shows a state in which a semiconductor chip 139' with a film adhesive is pulled away from the support sheet 10 in the direction of arrow I using a pulling mechanism 7 in the pickup (1) step. Examples of the pulling mechanism 7 include a vacuum collet chuck. The pulling mechanism 7 is not shown in cross section here. The film adhesive 130 is prevented from remaining on the first surface 10a of the support sheet 10. FIG6D shows a state in which a semiconductor chip 9' is bonded to the circuit forming surface 5a of the substrate 5 by the film adhesive 130 in the bonding step.

FIG6 shows the manufacturing method (1) when using a dicing wafer 101, but the same semiconductor device can be obtained when using other dicing wafers.

[Manufacturing method (2)] The film adhesive of one embodiment of the present invention can also be used in manufacturing a semiconductor device by attaching it to a semiconductor wafer before forming a dicing die of the embodiment of the present invention. As a manufacturing method of a semiconductor device in this case, for example, the following manufacturing method (sometimes referred to as "manufacturing method (2)" in this specification) can be listed, which comprises: a lamination step (21) of using the film adhesive to manufacture a laminate (21), wherein the laminate (21) comprises a semiconductor wafer and the film adhesive disposed on the inner surface of the semiconductor wafer; a lamination step (22) of laminating the laminate (21) A cutting sheet is attached to the surface (i.e., the second surface) of the aforementioned film adhesive in the opposite side to the aforementioned semiconductor wafer side, thereby producing a laminate (22) in which the aforementioned cutting sheet and the laminate (21) are sequentially laminated (in other words, the aforementioned cutting sheet, the film adhesive and the semiconductor wafer are sequentially laminated in the thickness direction of these layers); a splitting/cutting step is to split the aforementioned semiconductor wafer in the aforementioned laminate (22), thereby A semiconductor chip is manufactured and the film adhesive is cut along the division portion of the semiconductor wafer to manufacture a semiconductor chip assembly (2) with a film adhesive. The semiconductor chip assembly (2) with a film adhesive is composed of a plurality of semiconductor chips with a film adhesive formed by the semiconductor chip and the cut film adhesive disposed on the inner surface of the semiconductor chip and held on the cutting sheet. ; the picking up step (2) is to pull the film-bonded semiconductor chip in the aforementioned film-bonded semiconductor chip assembly (2) away from the aforementioned dicing sheet and pick it up, thereby obtaining the film-bonded semiconductor chip; and the die bonding step is to bond the obtained semiconductor chip in the aforementioned film-bonded semiconductor chip to the circuit forming surface of the substrate using the film adhesive in the aforementioned film-bonded semiconductor chip. In the manufacturing method (2), except for using the film adhesive of one embodiment of the present invention instead of the previous film adhesive, the semiconductor device can be manufactured using the same method as the previous method.

[Lamination (21) Step] In the aforementioned lamination (21) step, one side (i.e., the first side) of the aforementioned film adhesive is attached to the inner surface of the semiconductor wafer, thereby producing a laminate (21). This step can be performed using the same method as the previous method of attaching the film adhesive to the inner surface of the semiconductor wafer, except that the film adhesive of one embodiment of the present invention is used instead of the previous film adhesive.

[Lamination (22) Step] In the aforementioned lamination (22) step, a cutting sheet is attached to the exposed surface (i.e., the second surface) of the film adhesive in the aforementioned laminate (21), thereby producing the laminate (22). The cutting sheet used in this step can be a known cutting sheet, and the cutting sheet can be attached to the film adhesive using known methods.

The aforementioned dicing sheet is substantially the same as the support sheet used in the dicing adhesive wafer used in the manufacturing method (1). Therefore, the laminate (22) obtained in this step is substantially the same as the laminate (1) obtained in the manufacturing method (1).

[Division/cutting step] In the aforementioned division/cutting step, the division of the semiconductor wafer in the laminate (22) (manufacturing of semiconductor chips) and the cutting of the film adhesive in the laminate (22) can be performed in the same manner as the division of the semiconductor wafer in the laminate (1) and the cutting of the film adhesive in the laminate (1) in the manufacturing method (1).

The semiconductor chip with a film adhesive produced in this step is the same as the semiconductor chip with a film adhesive produced in the dividing/cutting step of the manufacturing method (1). In the semiconductor chip assembly (2) with a film adhesive produced in this step, a plurality of semiconductor chips with a film adhesive are held (fixed) on the aforementioned dicing sheet in an orderly arranged state. Furthermore, the semiconductor chip assembly (2) with a film adhesive is substantially the same as the semiconductor chip assembly (1) with a film adhesive produced in the dividing/cutting step of the manufacturing method (1).

[Pick-up (2) step] In the aforementioned pick-up (2) step, the semiconductor chip with a film adhesive in the semiconductor chip assembly with a film adhesive (2) can be pulled off from the dicing sheet and picked up by a known method. The pick-up (2) step can be performed by the same method as the pick-up (1) step in the manufacturing method (1), except that the semiconductor chip assembly with a film adhesive (2) is used instead of the semiconductor chip assembly with a film adhesive (1).

In this step, by using the film adhesive of one embodiment of the present invention, even if the dicing wafer does not have an adhesive layer for direct contact with the film adhesive, it is possible to suppress the film adhesive from remaining on the dicing wafer when picking up a semiconductor wafer with the film adhesive.

[Die bonding step] The above-mentioned die bonding step is the same as the die bonding step in the manufacturing method (1).

After the die bonding step, a semiconductor package and a semiconductor device can be manufactured by the same method as in the manufacturing method (1).

FIG7 is a cross-sectional view for schematically illustrating the manufacturing method (2). Here, the manufacturing method (2) is shown when the film adhesive 13 shown in FIG3 is used.

FIG7A shows a laminate (21) 129A obtained in the lamination step (21). The laminate (21) 129A comprises a semiconductor wafer 9 and a film adhesive 13 disposed on the inner surface 9b of the semiconductor wafer 9. FIG7B shows a laminate (22) 129B obtained in the lamination step (22). The laminate (22) 129B is formed by laminating a dicing sheet 20, a film adhesive 13, and a semiconductor wafer 9 in this order in the thickness direction of these layers. FIG7C shows a semiconductor chip assembly (2) 129C having a film adhesive obtained in the segmentation/cutting step. The semiconductor chip assembly (2) 129C with a film adhesive is composed of a plurality of semiconductor chips 139' with a film adhesive formed by a semiconductor chip 9' and a film adhesive 130 provided on the inner surface 9b' of the semiconductor chip 9' after cutting, and is held on the dicing sheet 20. Figure 7D shows the state in which the semiconductor chip 139' with a film adhesive is pulled away from the dicing sheet 20 in the direction of arrow I using the pulling mechanism 7 in the picking (2) step. The residue of the film adhesive 130 on the first surface 20a of the dicing sheet 20 is suppressed. FIG7E shows the state in which the semiconductor chip 9' is bonded to the circuit-forming surface 5a of the substrate 5 via a film-like adhesive 130 during the die bonding step. [Embodiment]

The present invention will be described in more detail below with reference to specific embodiments. However, the present invention is not limited to the embodiments shown below.

[Resin Raw Materials] The following are the formal names of the resin raw materials referred to in the Examples and Comparative Examples. BA: n-butyl acrylate MA: methyl acrylate GMA: glycidyl methacrylate HEA: 2-hydroxyethyl acrylate MMA: methyl methacrylate AA: acrylic acid

[Raw Materials for Adhesive Composition Production] The following are the raw materials used to produce the adhesive composition. [Polymer Component (a)] (a)-1: Acrylic resin (weight-average molecular weight 800,000, glass transition temperature -28°C) obtained by copolymerizing BA (55 parts by mass), MA (10 parts by mass), GMA (20 parts by mass), and HEA (15 parts by mass). (a)-2: Acrylic resin (weight-average molecular weight 800,000, glass transition temperature -42°C) obtained by copolymerizing BA (84 parts by mass), MMA (8 parts by mass), AA (3 parts by mass), and HEA (5 parts by mass). (a)-3: Acrylic resin with a weight-average molecular weight of 700,000. [Epoxy resin (b1)] (b1)-1: A mixture of liquid bisphenol A epoxy resin and acrylic rubber particles ("BPA328" manufactured by Japan Catalyst Co., Ltd., epoxy equivalent weight 235 g/eq) (b1)-2: Bisphenol A epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, softening point 93°C, epoxy equivalent weight 800 g/eq to 900 g/eq) (b1)-3: o-cresol novolac epoxy resin (Japan (EOCN-104S manufactured by Nippon Kayaku Co., Ltd., softening point 90°C to 94°C, epoxy equivalent weight 213g/eq to 223g/eq) (b1)-4: Liquid bisphenol F epoxy resin (YL983U manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent weight 165g/eq to 175g/eq) (b1)-5: o-Cresol novolac epoxy resin (EOCN-102S manufactured by Nippon Kayaku Co., Ltd., softening point 55°C to 7 7°C, epoxy equivalent weight 205 g/eq to 217 g/eq) (b1)-6: Trisphenol-based epoxy resin ("EPPN-502H" manufactured by Nippon Kayaku Co., Ltd., softening point 54°C, epoxy equivalent weight 167 g/eq) (b1)-7: Liquid bisphenol A epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 184 g/eq to 194 g/eq) (b1)-8: o-cresol novolac epoxy resin ("EOCN-103S" manufactured by Nippon Kayaku Co., Ltd., softening point 81°C to 85°C, epoxy equivalent weight 209g/eq to 219g/eq) (b1)-9: Dicyclopentadiene epoxy resin ("XD-1000" manufactured by Nippon Kayaku Co., Ltd., softening point 68°C to 78°C, epoxy equivalent weight 245g/eq to 260g/eq) (b1)-10: Dicyclopentadiene epoxy resin ("EPICLON" manufactured by DIC Corporation) HP-7200HH, softening point 88°C to 98°C, epoxy equivalent weight 274g/eq to 286g/eq) [Thermohardener (b2)] (b2)-1: Dicyandiamide (Adeka Hardener EH-3636AS, manufactured by ADEKA Corporation, solid dispersion type latent hardener, softening point 209°C, active hydrogen content 21g/eq) (b2)-2: o-Cresol novolac resin (DIC Corporation, Phenolite KA-1160, softening point 80°C, hydroxyl equivalent weight 117g/eq) [Hardening accelerator (c)] (c)-1: 2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemical Industries, Ltd., Curezol 2PHZ-PW”) [Filler (d)] (d)-1: Epoxy-modified spherical silica (Admatechs "ADMANANO YA050C-MKK", average particle size 50 nm) [Coupling agent (e)] (e)-1: Silicate compound formed by adding 3-glycidyloxypropyltrimethoxysilane (Mitsubishi Chemical Corporation "MKC Silicate MSEP-2") (e)-2: Oligomer-type silane coupling agent with epoxy, methyl, and methoxy groups (Shin-Etsu "X-41-1056" manufactured by Silicones, epoxy equivalent weight 280 g/eq) [Crosslinking agent (f)] (f)-1: Trihydroxymethylpropane-toluene diisocyanate trimer adduct ("Coronate L" manufactured by Tosoh Corporation) [Energy ray curing resin (g)] (g)-1: A mixture of dipentaerythritol hexaacrylate (a hexafunctional UV-curable compound with a molecular weight of 578) and dipentaerythritol pentaacrylate (a pentafunctional UV-curable compound with a molecular weight of 525) ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.) (g)-2: Tricyclodecane dihydroxymethyl diacrylate ("KAYARAD R-684, molecular weight 304) [Photopolymerization initiator (h)] (h)-1: 1-Hydroxycyclohexylphenyl ketone ("IRGACURE (registered trademark) 184" manufactured by BASF)

[Example 1] [Preparation of Film Adhesive] [Preparation of Adhesive Composition] Polymer component (a)-1 (20 parts by mass), epoxy resin (b1)-1 (25 parts by mass), epoxy resin (b1)-2 (35 parts by mass), epoxy resin (b1)-3 (8 parts by mass), thermosetting agent (b2)-1 (1.5 parts by mass), curing accelerator (c)-1 (1.5 parts by mass), A coupling agent (e)-1 (0.6 parts by mass), a crosslinking agent (f)-1 (0.2 parts by mass), an energy-ray-curable resin (g)-1 (8 parts by mass), and a photopolymerization initiator (h)-1 (0.2 parts by mass) were dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to produce a thermosetting adhesive composition having a total concentration of 50% by mass of all components other than the solvent. The amounts of the components other than the solvent listed here are all amounts for the target product without the solvent.

[Manufacturing of Film-like Adhesive] A release film made of polyethylene terephthalate (SP-PET381031, manufactured by Lintec, 38 μm thick) with one side treated with silicone was used. The adhesive composition obtained above was applied to the release-treated surface of the release film and dried at 100°C for 1 minute to produce a 20 μm thick thermosetting film-like adhesive.

[Manufacturing of Dicing Adhesive Sheets] A laminated substrate ("HUSL1302" manufactured by Achilles, 100μm thick, sometimes referred to as the "PP/EMAA laminated substrate") is used as the substrate. The exposed side of the film-like adhesive obtained above, opposite to the side with the release film, is attached to the surface of the polypropylene layer to produce the dicing adhesive sheet. This dicing adhesive sheet is composed solely of a support sheet made of the substrate, a film-like adhesive, and a release film, laminated in this order along the thickness direction of these layers.

[Evaluation of Film Adhesive] [Determination of _D0 ] [Preparation of First Test Piece] Using the same method as above, two sheets of film adhesive were prepared, each with a release film on one side. These two sheets were then irradiated with UV light using a UV irradiation device ("RAD-2000 m/12" manufactured by Lintec) at an illuminance of 230 mW/ ^cm² and a light dose of 120 mJ/ ^cm² . The exposed surfaces of the two UV-irradiated sheets were then bonded together to form a 40 μm thick laminate of two films with release films on both sides (primary laminate). Then, make two sheets of this primary layer.

Next, the release film was removed from one side of these two primary laminates, and the exposed surfaces of the newly formed film adhesive were bonded together, thereby producing four film adhesive laminates (secondary laminates) with a thickness of 80 μm and release films on both sides. Two more secondary laminates were then produced. Next, the release film was removed from one side of these two secondary laminates, and the exposed surfaces of the newly formed film adhesive were bonded together, thereby producing eight film adhesive laminates (tertiary laminates) with a thickness of 160 μm and release films on both sides. Next, using this tertiary laminate and the previously described primary laminate, the release film was removed from one side of these laminates, and the exposed surfaces of the newly produced film adhesive were bonded together. This produced 10 film adhesive laminates (quadruple laminates) with a thickness of 200 μm and release films on both sides.

The obtained quadruple laminate was punched out using a dumbbell cutting machine ("SDBK-1000" manufactured by DUMBBELL) in the same shape and size as the test piece specified in JIS K7128-3 to produce the first test piece (thickness 200 μm).

[D ₀ Determination] The first specimen obtained above was subjected to a tear test in accordance with JIS K7128-3 using a universal tensile testing machine ("AG-IS" manufactured by Shimadzu Corporation) to determine D ₀ . The distance between the clamps in the first specimen was set to 60 mm, the tear rate was set to 200 mm/min, and the sampling time was set to 10 ms. The results are shown in Table 1.

[Calculation of |ΔT|] When measuring D ₀ as described above, T _max , D ₁ , and 0.6D ₁ were measured simultaneously, and |ΔT| was calculated based on these values. The results are shown in Table 1.

[Evaluation of the Effectiveness of Suppressing Film Adhesive Residue During Pickup] [Production of Silicon Wafers with Film Adhesive] The peeling film was removed from the film adhesive on the dicing wafer obtained above. Using a laminating machine ("Adwill RAD2500" manufactured by Lintec), the exposed surface of the film adhesive on the dicing wafer after the peeling film was removed was bonded to the polished surface of a silicon wafer (200 mm diameter, 350 μm thickness) with a #2000 internal polish. The dicing wafer was then secured to a wafer dicing ring frame.

Next, the film-shaped adhesive was irradiated with ultraviolet light using an ultraviolet irradiation device ("RAD-2000 m/12" manufactured by Lintec Corporation) at an illumination of 230 mW/cm ² and a light dose of 120 mJ/cm ² .

Next, a dicing device ("DFD6361" manufactured by DISCO) was used to continuously separate the silicon wafer and cut the film adhesive, obtaining silicon wafers measuring 2 mm x 2 mm. The dicing was performed by setting the dicing blade's travel speed to 30 mm/sec and its rotational speed to 30,000 rpm. The dicing blade cut into the wafer to a depth of 20 μm from the film adhesive bonding surface of the wafer's substrate (i.e., the entire thickness of the film adhesive and a depth of 20 μm from the film adhesive side of the substrate). The dicing blade used was the "Z05-SD2000-D1-90 CC" manufactured by DISCO. Through the above steps, a group of silicon wafers with film adhesive is manufactured using a dicing adhesive wafer. The group of silicon wafers with film adhesive is composed of a silicon wafer and a film adhesive disposed on the inner surface of the silicon wafer. The plurality of silicon wafers with film adhesive are fixed on a substrate in an orderly arranged state by the film adhesive.

[Evaluation of the Effect of Suppressing Film Adhesive Residue During Pickup] Using a pick-and-bond device ("BESTEM D-02" manufactured by Canon Machinery), the film-coated silicon wafers obtained above were separated from the substrate and picked up. This picking-up was performed on 100 film-coated silicon wafers, with each film-coated silicon wafer being lifted from the film side using a lift pin. Next, using a digital microscope (Keyence VHX-1000), the pick-up locations on the support sheet (substrate) were observed. The number of locations where film adhesive residues of 100 μm or more were counted. The effectiveness of suppressing film adhesive residue during pick-up was evaluated based on the following criteria. The results are shown in Table 1. The parenthesized values within the corresponding columns in Table 1 represent the number of locations where the film adhesive residues were present. [Evaluation Criteria] A: 5 or fewer locations with film adhesive residues. B: 6 or more locations with film adhesive residues.

[Measurement of Adhesion Strength of Cured Film Adhesives] [Manufacturing of Silicon Wafers with Film Adhesives] A group of silicon wafers with film adhesives were manufactured using the same method as described above for "Evaluation of the Effectiveness of Suppressing Film Adhesive Residue During Pickup."

[Preparation of the Second Test Piece] Next, a film-bonded silicon wafer from the group of film-bonded silicon wafers was removed from the substrate and picked up. Then, using a manual die bonder (CAMMAX Precima "EDB65"), the entire surface of the film-bonded silicon wafer (the surface opposite the silicon wafer) with the exposed film adhesive was press-bonded to the surface of a copper plate (500 μm thick), thereby bonding the film-bonded silicon wafer to the copper plate. Die bonding was performed as follows: A force of 2.45 N (250 gf) was applied to the silicon wafer with film adhesive heated to 125°C for 3 seconds in a direction perpendicular to the contact surface between the wafer and the copper plate. Then, the bonded copper plate was heated at 160°C for 1 hour to thermally cure the film adhesive on the copper plate. Through these steps, a second test piece was produced, consisting of a copper plate, a cured film adhesive, and a silicon wafer stacked sequentially along the thickness direction.

[Measurement of the Adhesion Strength of Thermally Cured Film Adhesives] Using a bond strength tester ("Series 4000" manufactured by Dage), a force was applied simultaneously at a rate of 200 μm/sec in a direction parallel to one side of the cured film adhesive on the second test piece obtained above, where the side surface was aligned with the side surface of the silicon wafer. A stainless steel flat-plate pressing mechanism was used as the force-applying mechanism. The tip of the copper plate side of the pressing mechanism was adjusted to a height of 7 μm from the surface of the copper plate side on which the silicon wafer was placed, so that the pressing mechanism was in contact with the copper plate. The maximum force applied until the hardened material was destroyed, peeled off the copper plate, or peeled off the silicon wafer was measured, and this value was used as the adhesion force of the hardened material (N/2mm). The results are shown in Table 1.

[Manufacturing of Film Adhesive, Manufacturing of Dicing Wafers, and Evaluation of Film Adhesive] [Example 2, Comparative Examples 1 and 2] A film adhesive and dicing wafer were manufactured and evaluated using the same method as in Example 1, except that the types and amounts of the components in the adhesive composition were adjusted to those shown in Table 1. Either or both of the types and amounts of the components used in manufacturing the adhesive composition were changed. However, in Example 2 and Comparative Example 1, where the adhesive composition did not contain the energy-beam-curable resin (g), the film-like adhesive was not irradiated with UV light when preparing the first test piece and the silicon wafer with the film-like adhesive. Furthermore, a polypropylene (PP) substrate ("FUNCRARE LLD#80" manufactured by GUNZE, 80 μm thick) was used as the substrate instead of the PP/EMAA laminate substrate. The results are shown in Table 1.

In addition, when "-" is written in the column of the contained ingredient in Table 1, it means that the adhesive composition does not contain the ingredient.

[Table 1] Example 1 Example 2 Comparative example 1 Comparative example 2 substrate PP/EMAA laminated base material PP base material PP base material PP/EMAA laminated base material Ingredients of adhesive composition (by mass) Polymer component (a) (a)-1 20 - - 12 (a)-2 - twenty three - - (a)-3 - - 13 - Epoxy resin (b1) (b1)-1 25 - - twenty two (b1)-2 35 - - - (b1)-3 8 - - - (b1)-4 - 5 - - (b1)-5 - 30 - - (b1)-6 - 15 - - (b1)-7 - - twenty three - (b1)-8 - - twenty three - (b1)-9 - - - 18 (b1)-10 - - - 38 Heat hardener (b2) (b2)-1 1.5 - - 0.5 (b2)-2 - 24.8 22.8 - Hardening accelerator (c) (c)-1 1.5 0.2 0.2 0.5 Filling material (d) (d)-1 - - 17 - Coupling agent (e) (e)-1 0.6 - - 0.6 (e)-2 - 1 1 - Crosslinking agent (f) (f)-1 0.2 1 - 0.2 Energy ray curing resin (g) (g)-1 8 - - - (g)-2 - - - 8 Photopolymerization initiator (h) (h)-1 0.2 - - 0.2 Evaluation results D ₀ (mm) 14.2 9.2 167.2 27.5 |ΔT|(N/mm)(ΔT(N/mm)) 2.1(2.1) 2.3(-2.3) 9.8(9.8) 10.2(10.2) Suppresses the effect of film adhesive residue during pickup A(3) A(0) B(18) B(32) Adhesion strength of cured film adhesive (N/2mm□) 111 154 249 57

The above results clearly demonstrate that, even when the support sheet lacks an adhesive layer in direct contact with the film adhesive, Examples 1 and 2 can suppress film adhesive residue on the support sheet when picking up a silicon wafer coated with the film adhesive. In Examples 1 and 2, _D0 is 14.2 mm or less. Furthermore, in Examples 1 and 2, the adhesive strength of the cured film adhesive is 111 N/2 mm or greater, indicating sufficient adhesive strength. Furthermore, in these Examples, the cured film adhesive did not peel off the silicon wafer during the aforementioned adhesive force measurement. Furthermore, in Examples 1 and 2, |ΔT| is 2.3 or less.

In contrast, in Comparative Examples 1 and 2, when picking up silicon wafers coated with film adhesive, it was impossible to prevent film adhesive residue from remaining on the support sheet. In Comparative Examples 1 and 2, D ₀ was greater than 27.5 mm. Furthermore, in Comparative Example 2, the bonding force of the cured film adhesive was 57 N/2 mm, indicating insufficient bonding force. Meanwhile, in Comparative Example 1, |ΔT| was a relatively large 10.2. [Industrial Applicability]

The present invention can be used to manufacture semiconductor devices.

5: Substrate 5a: Circuit-forming surface of substrate 7: Pull-off mechanism 8: Pressing mechanism 9: Semiconductor wafer 9': Semiconductor chip 9b: Inner surface of semiconductor wafer 9b': Inner surface of semiconductor chip 10: Support sheet 10a: First surface of support sheet 11: Base material 11a: First surface of base material 13: Film adhesive 13a: First surface of film adhesive 13b: Second surface of film adhesive 15: Peeling film 16: Jig adhesive layer 16a: Top and side surfaces of jig adhesive layer 20: Dicing blade 20a: First surface of dicing blade 90: Cured film adhesive 90a: Curing of film adhesive 1st surface of the object 90b: 2nd surface of the cured film adhesive 90c: Side surface of the cured film adhesive 91: Copper plate 92: Silicon wafer 92c: Side surface of the silicon wafer 99: 1st test piece 101, 102: Diced adhesive wafer 119A: Laminated body (1) 119B: Semiconductor with film adhesive Chip assembly (1) 129A: Laminated body (21) 129B: Laminated body (22) 129C: Semiconductor chip assembly with film adhesive (2) 130: Film adhesive after cutting 139': Semiconductor chip with film adhesive 151: First peeling film 152: Second peeling film P: Force

[Figure 1] is a top view of a first test piece produced using a film adhesive according to an embodiment of the present invention. [Figure 2] is a cross-sectional view schematically illustrating a method for measuring the bonding strength of a cured product of a film adhesive according to an embodiment of the present invention. [Figure 3] is a cross-sectional view schematically illustrating an example of a film adhesive according to an embodiment of the present invention. [Figure 4] is a cross-sectional view schematically illustrating an example of a dicing adhesive sheet according to an embodiment of the present invention. [Figure 5] is a cross-sectional view schematically illustrating another example of a dicing adhesive sheet according to an embodiment of the present invention. [Figure 6A] is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor device using a dicing adhesive sheet according to an embodiment of the present invention. FIG6B is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor device using a dicing wafer according to an embodiment of the present invention. FIG6C is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor device using a dicing wafer according to an embodiment of the present invention. FIG6D is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor device using a dicing wafer according to an embodiment of the present invention. FIG7A is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor device using a film adhesive according to an embodiment of the present invention. FIG7B is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor device using a film adhesive according to an embodiment of the present invention. [Figure 7C] is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor device using a film-shaped adhesive according to an embodiment of the present invention. [Figure 7D] is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor device using a film-shaped adhesive according to an embodiment of the present invention. [Figure 7E] is a cross-sectional view schematically illustrating an example of a method for manufacturing a semiconductor device using a film-shaped adhesive according to an embodiment of the present invention.

13: Film adhesive

13a: First side of film adhesive

13b: Second side of film adhesive

151: First peeling membrane

152: Second peeling membrane

Claims (4)

A film-like adhesive is a curable film-like adhesive; for a first test piece which is a laminate of a plurality of sheets of the aforementioned film-like adhesive and has a thickness of 200 μm, in accordance with JIS K7128-3, the distance between a pair of clamps for clamping and fixing the aforementioned first test piece is set to 60 mm, and the tearing speed is set to 200 mm/min. When a tearing test is performed by a right-angle tearing method, the displacement of the aforementioned first test piece in the tearing direction from the time the tear strength of the aforementioned first test piece reaches a maximum to the time the aforementioned first test piece breaks is less than 15 mm; the aforementioned film-like adhesive contains an acrylic resin and one or more selected from an o-cresol novolac-type epoxy resin and an o-cresol novolac resin; and the aforementioned film-like adhesive does not contain a filler. The film adhesive described in claim 1 is used to prepare a second test piece, wherein the second test piece comprises a cured product of the film adhesive having a size of 2 mm × 2 mm and a thickness of 20 μm, a copper plate having a thickness of 500 μm and disposed entirely on one surface of the cured product, and a silicon wafer having a thickness of 350 μm and disposed entirely on the other surface of the cured product, wherein the side surface of the cured product and the side surface of the silicon wafer are aligned; With the copper plate fixed, a force is applied simultaneously at a rate of 200 μm/sec to the aligned portion of the side surface of the hardened material and the side surface of the silicon wafer in the second test piece in a direction parallel to one surface of the hardened material, until the hardened material is destroyed, or the hardened material is peeled off from the copper plate, or the hardened material is peeled off from the silicon wafer, with the maximum value of the force applied being 100 N/2 mm or more. A cutting adhesive chip, comprising a support sheet and a film adhesive disposed on one surface of the support sheet; the film adhesive is the film adhesive described in claim 1 or 2. As claimed in claim 3, the dicing adhesive chip, wherein the aforementioned support sheet is composed only of a substrate.