Method for manufacturing semiconductor device

Abstract

This method for manufacturing a semiconductor device includes the steps of: preparing a laminate having a dicing-die bonding integrated film including a base material layer, a pressure-sensitive adhesive layer and an adhesive layer, and a plurality of semiconductor chips obtained by dicing a semiconductor wafer; dicing the adhesive layer by expanding the adhesive layer of the laminate under a cooling condition to manufacture a semiconductor chip with an adhesive piece; picking up the semiconductor chip with the adhesive piece from the pressure-sensitive adhesive layer; and bonding the semiconductor chip with the adhesive piece having the semiconductor chip and the adhesive piece to a support member via the adhesive piece. The adhesive layer contains a thermosetting resin component and an elastomer and may further contain an inorganic filler. The content of the inorganic filler is 0-5% by mass based on the total amount of a film adhesive. The elastomer includes a predetermined (meth) acrylate polymer.

Description

Manufacturing method for semiconductor devices

[0001] This disclosure relates to a method for manufacturing a semiconductor device.

[0002] A dicing-die bonding integrated film is sometimes used in the manufacture of semiconductor devices (semiconductor packages), in which a dicing film having a base film and an adhesive layer for fixing the semiconductor wafer during the process of dicing the semiconductor wafer, and an adhesive layer (film-like adhesive) for bonding the semiconductor wafer to a support member or other semiconductor chips are integrated (for example, Patent Documents 1 and 2).

[0003] In recent years, methods such as SDBG (Stealth Dicing Before Grinding) and DBG (Dicing Before Grinding) have been put into practical use as methods for separating semiconductor wafers into individual chips (for example, Patent Document 3). The SDBG method involves forming a modified region inside the semiconductor wafer by irradiation with laser light, then grinding (polishing) the semiconductor wafer from the back side, and separating the semiconductor wafer into multiple semiconductor chips by cutting the wafer using the modified region as the dividing point. The DBG method involves forming a groove of a predetermined depth on the surface of the semiconductor wafer with a dicing blade or the like, and then grinding (polishing) the semiconductor wafer from the back side up to the groove to separate it into multiple semiconductor chips. An adhesive layer of a dicing-die bonding integrated film is attached to the multiple semiconductor chips separated by these methods under heating conditions. Next, the dicing film is expanded under cooling conditions (cooling expansion) to separate the adhesive layer into individual pieces, resulting in a semiconductor chip with adhesive pieces, each piece containing a semiconductor chip and the separated adhesive layer. Subsequently, the obtained semiconductor chip with adhesive pieces is picked up, mounted on a support member or another semiconductor chip, and bonded via the adhesive pieces to manufacture a semiconductor device.

[0004] Japanese Patent Publication No. 2019-175958, International Patent Publication No. 2018 / 105613, Japanese Patent Publication No. 2022-179420

[0005] The purpose of this disclosure is to provide a method for manufacturing a semiconductor device that exhibits excellent cooling and dissociation properties.

[0006] This disclosure provides a method for manufacturing a semiconductor device as described in [1] to [7]. [1] A step of preparing a laminate comprising a dicing-die bonding integrated film having a base layer, an adhesive layer, and an adhesive layer in this order, and a plurality of semiconductor chips formed by fragmenting a semiconductor wafer, provided on the adhesive layer of the dicing-die bonding integrated film; a step of expanding the adhesive layer of the laminate under cooling conditions to fragment a plurality of semiconductor chips with adhesive pieces; a step of picking up a first semiconductor chip and a first semiconductor chip with adhesive pieces having a first semiconductor chip and a first adhesive piece from the plurality of semiconductor chips with adhesive pieces from the adhesive layer; and a step of bonding the first semiconductor chip with adhesive pieces to a support member via the first adhesive piece, wherein the adhesive layer contains a thermosetting resin component and an elastomer, and may further contain an inorganic filler, the amount of the inorganic filler is 0 to 5% by mass based on the total amount of the adhesive layer, and the elastomer contains a (meth)acrylate polymer containing structural units derived from (meth)acrylate having epoxy groups. A method for manufacturing a semiconductor device, wherein the content of structural units derived from the epoxy group-containing (meth)acrylate is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer.[2] A step of preparing a laminate comprising a dicing-die bonding integrated film having a base layer, an adhesive layer, and an adhesive layer in this order, and a plurality of semiconductor chips formed by fragmenting a semiconductor wafer, provided on the adhesive layer of the dicing-die bonding integrated film; a step of expanding the adhesive layer of the laminate under cooling conditions to fragment a plurality of semiconductor chips with adhesive pieces; a step of picking up a first semiconductor chip and a first semiconductor chip with adhesive pieces having a first semiconductor chip and a first adhesive piece from the plurality of semiconductor chips with adhesive pieces from the adhesive layer; and a step of bonding the first semiconductor chip with adhesive pieces to a support member via the first adhesive piece, wherein the adhesive layer contains a thermosetting resin component and an elastomer, and may further contain an inorganic filler, the amount of the inorganic filler is 0 to 5% by mass based on the total amount of the adhesive layer, and the elastomer contains a (meth)acrylate polymer containing structural units derived from (meth)acrylate having epoxy groups. A method for manufacturing a semiconductor device, wherein the epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more.[3] A step of preparing a laminate comprising a dicing-die bonding integrated film having a base layer, an adhesive layer, and an adhesive layer in this order, and a plurality of semiconductor chips formed by fragmenting a semiconductor wafer, provided on the adhesive layer of the dicing-die bonding integrated film; a step of expanding the adhesive layer of the laminate under cooling conditions to fragment a plurality of semiconductor chips with adhesive pieces; a step of picking up a first semiconductor chip and a first semiconductor chip with adhesive pieces having a first semiconductor chip and a first adhesive piece from the plurality of semiconductor chips with adhesive pieces from the adhesive layer; and a step of bonding the first semiconductor chip with adhesive pieces to a support member via the first adhesive piece, wherein the adhesive layer contains a thermosetting resin component and an elastomer, and may further contain an inorganic filler, the amount of the inorganic filler is 0 to 5% by mass with respect to the total amount of the adhesive layer, and the elastomer contains a (meth)acrylate polymer containing structural units derived from (meth)acrylate having epoxy groups. A method for manufacturing a semiconductor device, wherein, in the infrared absorption spectrum of the (meth)acrylate polymer, when the area of ​​the absorption peak originating from the antisymmetric stretching of the epoxy group is P(A) and the area of ​​the absorption peak originating from the stretching vibration of the carbonyl group is P(B), P(A) and P(B) satisfy the condition of the following formula (1): P(A) / P(B) ≥ 0.0055 (1) [4] A method for manufacturing a semiconductor device according to any one of [1] to [3], wherein the thickness of the adhesive layer is 15 μm or less. [5] A method for manufacturing a semiconductor device according to any one of [1] to [4], further comprising the steps of: thermally curing the first adhesive piece in the first adhesive piece-attached semiconductor chip at a temperature of 100 to 180°C for 15 to 60 minutes; and electrically connecting the first semiconductor chip and the support member with a bonding wire. [6] A method for manufacturing a semiconductor device according to any one of [1] to [5], further comprising the step of bonding a second semiconductor chip having a second semiconductor chip and a second adhesive piece, from among the plurality of semiconductor chips with adhesive pieces, to the surface of the first semiconductor chip with adhesive piece bonded to the support member, via the second adhesive piece.[7] A method for manufacturing a semiconductor device according to [6], further comprising: a step of thermally curing the first adhesive piece in the first adhesive piece-attached semiconductor chip and the second adhesive piece in the second adhesive piece-attached semiconductor chip at a temperature of 100 to 180°C for 15 to 60 minutes; and a step of electrically connecting the first semiconductor chip and the second semiconductor chip with the support member using bonding wires.

[0007] According to this disclosure, a method for manufacturing a semiconductor device that exhibits excellent cooling and dissociation properties is provided.

[0008] Figure 1 is a schematic cross-sectional view showing one embodiment of a semiconductor device. Figure 2 is a schematic cross-sectional view showing another embodiment of a semiconductor device. Figure 3 is a schematic cross-sectional view showing another embodiment of a semiconductor device. Figure 4 is a schematic cross-sectional view showing one embodiment of a dicing-die bonding integrated film. Figure 5 is a schematic perspective view showing the state in which the indentation plate has descended toward a sample fixed to a frame plate. Figure 6(a) is a schematic perspective view showing an example of an indentation plate, and Figure 6(b) is a cross-sectional view showing an enlarged view of the tip of the indentation plate shown in Figure 6(a). Figure 7 is a schematic cross-sectional view showing the state in which a load is applied to the sample by the indentation plate. Figure 8 is a schematic graph showing an example of the results of a cleavage test.

[0009] Embodiments of the present disclosure will be described below with reference to the drawings as appropriate. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including steps, etc.) are not essential unless otherwise specified. The sizes of the components in each figure are conceptual, and the relative relationships of the sizes of the components are not limited to those shown in each figure.

[0010] The same applies to numerical values ​​and their ranges in this disclosure, and this disclosure is not limited. Numerical ranges indicated using “~” in this specification indicate a range that includes the numerical values ​​before and after “~” as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another stepwise described numerical range. Also, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. Furthermore, the upper and lower limits stated individually can be combined in any way. Also, “A or B” means that either A or B is included, or both are included. Furthermore, unless otherwise specified, the materials exemplified below may be used individually or in combination of two or more. The content of each component in the composition means the total amount of multiple substances present in the composition if there are multiple substances corresponding to each component in the composition, unless otherwise specified.

[0011] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl group and (meth)acrylate polymer.

[0012] [Semiconductor Device] Figure 1 is a schematic cross-sectional view showing one embodiment of a semiconductor device. The semiconductor device 100 shown in Figure 1 comprises a semiconductor chip 11 (first semiconductor chip), a support member 12 on which the semiconductor chip 11 is mounted, and an adhesive member 15. The adhesive member 15 is provided between the semiconductor chip 11 and the support member 12 and adheres the semiconductor chip 11 and the support member 12. The adhesive member 15 is a cured product of an adhesive composition (a cured product of a film-like adhesive). The connection terminals (not shown) of the semiconductor chip 11 are electrically connected to external connection terminals (not shown) via bonding wires 13, and the semiconductor chip 11 and the bonding wires 13 are sealed by a sealing material 14.

[0013] Figure 2 is a schematic cross-sectional view showing another embodiment of a semiconductor device. In the semiconductor device 110 shown in Figure 2, the first semiconductor chip 11a (first semiconductor chip) is bonded to a support member 12 on which terminals 16 are formed by an adhesive member 15a (cured product of an adhesive composition (cured product of a film-like adhesive)), and the second semiconductor chip 11b (second semiconductor chip) is further bonded to the first semiconductor chip 11a by an adhesive member 15b (cured product of an adhesive composition (cured product of a film-like adhesive)). The connection terminals (not shown) of the first semiconductor chip 11a and the second semiconductor chip 11b are electrically connected to an external connection terminal via a bonding wire 13, and the semiconductor chips 11a, 11b and the bonding wire 13 are sealed by a sealing material 14. The semiconductor device 110 shown in Figure 2 can also be described as the semiconductor device 100 shown in Figure 1 further comprising another semiconductor chip (11b) stacked on the surface of the semiconductor chip (11a).

[0014] Figure 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device. The semiconductor device 120 shown in Figure 3 comprises a support member 12 and semiconductor chips 11a (first semiconductor chip), 11b (second semiconductor chip), 11c (third semiconductor chip), 11d (fourth semiconductor chip), 11e (fifth semiconductor chip), 11f (sixth semiconductor chip), 11g (seventh semiconductor chip), and 11h (eighth semiconductor chip) stacked on the support member 12. The four semiconductor chips 11a, 11b, 11c, and 11d are stacked at positions offset from each other in the lateral direction (a direction perpendicular to the stacking direction) for connection to connection terminals (not shown) formed on the surface of the support member 12. The four semiconductor chips 11e, 11f, 11g, and 11h stacked on top of them are stacked in a folded manner at positions offset from each other in the lateral direction (a direction perpendicular to the stacking direction) on the opposite side of the four semiconductor chips 11a, 11b, 11c, and 11d for connection to connection terminals (not shown) formed on the surface of the support member 12 (see Figure 3). The semiconductor chip 11a is bonded to the support member 12 by adhesive member 15a (cured product of adhesive composition (cured product of film-like adhesive)), and adjacent semiconductor chips are also bonded to each other by adhesive members 15b, 15c, 15d, 15e, 15f, 15g, and 15h (cured products of adhesive composition (cured product of film-like adhesive)). The connection terminals (not shown) of the semiconductor chips 11a, 11b, 11c, 11d, 11e, 11f, 11g, and 11h are electrically connected to external connection terminals via bonding wires 13, and the semiconductor chips 11a, 11b, 11c, 11d, 11e, 11f, 11g, and 11h are sealed by a sealing material 14. The semiconductor device 120 shown in Figure 3 can also be described as further comprising other semiconductor chips (11b, 11c, 11d, 11e, 11f, 11g, and 11h) stacked on the surface of the semiconductor chip (11a) in the semiconductor device 100 shown in Figure 1. The semiconductor device 120 shown in Figure 3 can also be described as having a folded structure in the stacked structure of the semiconductor chips.

[0015] Chip cracks that occur when connecting semiconductor chips with bonding wires are most likely to occur in semiconductor chips where there is no support (e.g., another semiconductor chip) below the connection terminal. For example, in the semiconductor device 120 shown in Figure 3, the semiconductor chip 11e (the fifth semiconductor chip) is stacked in a position shifted laterally (in a direction perpendicular to the stacking direction) relative to the semiconductor chip 11d (the fourth semiconductor chip) in a folded manner (see Figure 3), and there is no supporting semiconductor chip 11d (the fourth semiconductor chip) below the connection terminal of the semiconductor chip 11e (the connection point of the bonding wire 13, not shown). Therefore, in the semiconductor device 120 shown in Figure 3, chip cracks are most likely to occur when connecting the connection terminal of the semiconductor chip 11e (the fifth semiconductor chip) with the bonding wire 13. The cured film-like adhesive of this embodiment, described later, is expected to have a sufficient storage modulus, and is expected to suppress chip cracks caused by vibrations during wire bonding, even in locations where chip cracks are prone to occur.

[0016] Although the embodiments of the present disclosure have been described in detail above, the present disclosure is not limited to the above embodiments. For example, Figure 3 illustrates a semiconductor device in which eight semiconductor chips are stacked, but the number of stacked semiconductor chips is not limited to this. Also, Figure 3 illustrates a semiconductor device in which the semiconductor chips are stacked at positions offset from each other in the lateral direction (a direction perpendicular to the stacking direction), but a semiconductor device in which the semiconductor chips are stacked at positions not offset from each other in the lateral direction (a direction perpendicular to the stacking direction) is also possible.

[0017] [Method for Manufacturing a Semiconductor Device] The semiconductor device (semiconductor package) shown in Figures 1, 2, and 3 can be obtained, for example, by a method comprising: a step of preparing a laminate comprising the above-mentioned dicing-die bonding integrated film and a plurality of semiconductor chips formed by framing a semiconductor wafer and provided on the adhesive layer of the dicing-die bonding integrated film (laminated laminate manufacturing step); a step of expanding the adhesive layer of the laminate under cooling conditions to frame it and produce a plurality of semiconductor chips with adhesive pieces (cooling and expanding step); a step of picking up a first semiconductor chip and a first semiconductor chip with adhesive pieces having a first adhesive piece from the plurality of semiconductor chips with adhesive pieces from the adhesive layer (pickup step); and a step of bonding the first semiconductor chip with adhesive pieces to a support member via the first adhesive piece (first bonding step). A semiconductor device manufacturing method may further include a step (second bonding step) of bonding a second semiconductor chip and a second adhesive chip, which have the second adhesive chip, to the surface of a first semiconductor chip in a first adhesive chip bonded to a support member via the second adhesive chip. A semiconductor device manufacturing method may further include a thermosetting step, a wire bonding step, a sealing step, a post-curing step, a heat melting step, and so on.

[0018] In the laminate manufacturing process, semiconductor chips are formed by separating semiconductor wafers into individual pieces. The semiconductor wafer may be a silicon wafer, and the semiconductor chip may be a silicon chip.

[0019] The thickness of the semiconductor wafer may be, for example, 50 to 3000 μm, 100 to 2000 μm, or 200 to 1500 μm.

[0020] The method for dicing semiconductor wafers may be a stealth dicing method such as the SDBG (Steel Dicing Before Grinding) method, or a half-cut dicing method such as the DBG (Dicing Before Grinding) method.

[0021] The stealth dicing method may include, for example, the steps of: attaching a protective tape (backgrind tape) to the circuit surface of a semiconductor wafer; forming a modified region inside the semiconductor wafer by irradiating it with laser light; and grinding the semiconductor wafer from the back side and cutting the semiconductor wafer using the modified region as the dividing point.

[0022] The half-cut dicing method may include, for example, the steps of forming grooves on the surface of a semiconductor wafer with a dicing blade, attaching protective tape (backgrind tape) to the circuit surface of the semiconductor wafer, and grinding the semiconductor wafer from the back side up to the grooves.

[0023] By this method of separating semiconductor wafers into individual pieces, a laminate can be obtained comprising a protective tape and a plurality of semiconductor chips provided on the protective tape. In this laminate, the semiconductor chips are provided on the protective tape.

[0024] The thickness of the semiconductor chip may be less than the thickness of the semiconductor wafer, for example, 10 to 200 μm. The thickness of the semiconductor chip may be 15 μm or more, 20 μm or more, 150 μm or less, 100 μm or less, or 50 μm or less.

[0025] Next, a predetermined dicing-die bonding integrated film is prepared. The inventors' studies have shown that using a predetermined dicing-die bonding integrated film tends to improve the cooling-disconnectivity (disconnectivity when cooling-expanding) of the semiconductor device manufacturing method. Next, the adhesive layer of the dicing-die bonding integrated film is attached to the semiconductor chip under heating conditions, with the adhesive layer of the film in contact with the main surface of the semiconductor chip. The heating temperature may be, for example, 60 to 80°C. This allows for the creation of a laminate comprising the dicing-die bonding integrated film and a plurality of semiconductor chips, each formed by framing a semiconductor wafer, provided on the adhesive layer of the dicing-die bonding integrated film. Subsequently, a dicing ring is attached to the main surface of the adhesive layer on the adhesive layer side, surrounding the plurality of semiconductor chips. That is, the laminate may have a dicing ring on the main surface of the adhesive layer on the adhesive layer side. The protective tape is peeled off from the semiconductor chip at an appropriate time.

[0026] The specific dicing and die bonding integrated film and the film-like adhesive used in its adhesive layer will be described later.

[0027] The cooling and expanding process is a process of expanding (stretching) a dicing film by pushing up the area inside the dicing ring of the dicing film with a cooling stage under cooling conditions. The temperature under the cooling conditions may be, for example, -15 to 0°C. By expanding the dicing film, the adhesive layer is divided. This division results in the formation of multiple semiconductor chips with adhesive pieces on the adhesive layer, each having a semiconductor chip and adhesive pieces from which the adhesive layer has been separated.

[0028] After the cooling stage is lowered, the region of the dicing film between the dicing ring and the semiconductor chip with adhesive flap is heated by a heater. Due to the thermal contraction of the heated portion of the dicing film, the kerf width between the semiconductor chips with adhesive flap tends to widen further. The heating temperature when heating with the heater may be, for example, 200 to 270°C or 220 to 250°C.

[0029] The pickup process involves picking up semiconductor chips with adhesive pieces attached to a dicing / die bonding integrated film while separating the adhesive-piece attached semiconductor chips from each other, in order to detach the adhesive-piece attached semiconductor chips that are bonded and fixed to the integrated dicing / die bonding film. The method of expanding to separate the adhesive-piece attached semiconductor chips from each other is not particularly limited, and various conventionally known methods can be employed. For example, one method of separating the adhesive-piece attached semiconductor chips from each other is to expand the substrate layer. The expansion may be performed under cooling conditions as needed. The method of pickup is not particularly limited, and various conventionally known methods can be employed. For example, one method of pushing up individual adhesive-piece attached semiconductor chips from the dicing / die bonding integrated film side with a needle, and then picking up the pushed-up adhesive-piece attached semiconductor chips with a pickup device.

[0030] In this case, if the adhesive layer is radiation-curable (e.g., ultraviolet light), the pickup process can be performed after irradiating the adhesive layer with radiation. This reduces the adhesive strength of the adhesive layer to the adhesive chip, making it easier to peel off the semiconductor chip with the adhesive chip attached. As a result, pickup becomes possible without damaging the semiconductor chip with the adhesive chip attached.

[0031] The first bonding step is to bond a first semiconductor chip with adhesive pieces, from among a plurality of formed semiconductor chips with adhesive pieces, to a support member for mounting the first semiconductor chip via the first adhesive piece. The semiconductor device manufacturing method may optionally include a step (second bonding step) of bonding a second semiconductor chip with adhesive pieces, from among a plurality of semiconductor chips with adhesive pieces, to the surface of the first semiconductor chip bonded to the support member via the second adhesive piece. Both bonding can be performed by pressure bonding. The pressure bonding conditions are not particularly limited and can be set as appropriate and as needed. For example, the pressure bonding conditions may be a temperature of 80 to 160°C, a pressure of 0.05 to 0.5 MPa, and a time of 0.5 to 5 seconds. The support member may be an example of a support member similar to the one described above.

[0032] The method for manufacturing a semiconductor device may optionally include a step of further thermal curing of adhesive pieces (the first adhesive piece in the semiconductor chip with the first adhesive piece, and the second adhesive piece in the semiconductor chip with the second adhesive piece) or a film-like adhesive (thermal curing step). By further thermal curing the semiconductor chip (first semiconductor chip) and the support member, and the adhesive pieces (the first adhesive piece in the semiconductor chip with the first adhesive piece, and the second adhesive piece in the semiconductor chip with the second adhesive piece) that bond the semiconductor chip (first semiconductor chip) and the semiconductor chip (second semiconductor chip), stronger adhesion and fixation becomes possible. When thermal curing is performed, pressure may be applied simultaneously to cure the adhesive. The heating temperature in this step can be appropriately changed depending on the components constituting the adhesive piece. The heating temperature may be, for example, 60 to 200°C or 100 to 180°C. The temperature or pressure may be changed in stages. The heating time may be, for example, 1 to 120 minutes or 15 to 60 minutes.

[0033] The method for manufacturing a semiconductor device may, if necessary, include a step of electrically connecting a first semiconductor chip and a second semiconductor chip to a support member with a bonding wire, or more specifically, a step of electrically connecting an electrode pad on the semiconductor chip to the tip of a terminal portion (inner lead) of the support member with a bonding wire (wire bonding step). Examples of bonding wires include gold wire, aluminum wire, copper wire, etc. The temperature when performing wire bonding may be in the range of 80 to 250°C or 80 to 220°C. The heating time may be several seconds to several minutes. Wire bonding may be performed by a combination of ultrasonic vibration energy and applied pressure to create a bond while heated within the above temperature range.

[0034] A method for manufacturing a semiconductor device may optionally include a step of sealing a semiconductor chip with a sealing material (sealing step). This step is performed to protect the semiconductor chip or bonding wires mounted on a support member. This step can be performed by molding a sealing resin (sealing resin) in a mold. The sealing resin may be, for example, an epoxy resin. The heat and pressure during sealing allow the sealing resin to fill in irregularities on the support member and voids at the adhesive interface, thereby preventing delamination due to air bubbles at the adhesive interface.

[0035] The method for manufacturing a semiconductor device may, if necessary, include a step (post-curing step) to completely cure the sealing resin that is not sufficiently cured in the sealing step. Even if the adhesive piece is not heat-cured in the sealing step, in this step, the adhesive piece can be heat-cured along with the curing of the sealing resin, enabling adhesive fixation. The heating temperature in this step can be appropriately set depending on the type of sealing resin, and may be in the range of 165 to 185°C, for example, and the heating time may be 0.5 to 8 hours.

[0036] The method for manufacturing a semiconductor device may include a step of heating (heating and melting step) a semiconductor chip adhered to a support member or a semiconductor chip using a reflow furnace as needed. In this step, a resin-sealed semiconductor device may be surface-mounted on a mounting substrate such as a printed wiring board. Examples of the surface mounting method include reflow soldering in which solder is previously supplied on a printed wiring board and then heated and melted by hot air or the like to perform soldering. Examples of the heating method include hot air reflow, infrared reflow, etc. Also, the heating method may be one that heats the whole or one that heats a part. The heating temperature may be, for example, in the range of 240 to 280°C.

[0037] [Dicing and Die Bonding Integrated Film] FIG. 4 is a schematic cross-sectional view showing an embodiment of a dicing and die bonding integrated film. The dicing and die bonding integrated film 10 shown in FIG. 4 includes a base material layer 2, an adhesive layer 3, and an adhesive layer 1A composed of a film-like adhesive 1 in this order. The base material layer 2 and the adhesive layer 3 may be layers constituting the dicing film 4. When such a dicing and die bonding integrated film 10 is used, the lamination process on the semiconductor wafer becomes one time, so that the work efficiency can be improved. The dicing and die bonding integrated film may be in the form of a film, a sheet, a tape, or the like.

[0038] The dicing film 4 includes a base material layer 2 and an adhesive layer 3 provided on the base material layer 2.

[0039] The base layer 2 may be a base film. Examples of base materials for the base film include homopolymers and copolymers thereof of olefins such as ethylene, propylene, butene, hexene, methylpentene, 4-methyl-1-pentene, and vinyl acetate; polyesters such as polyethylene terephthalate and polyethylene naphthalate; ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and ethylene-(meth)acrylic acid-(meth)acrylic acid ester copolymer; and copolymers containing olefins such as ethylene and (meth)acrylic acid. Examples include ionomer resins having an ionic crosslinking structure formed by salt formation between the acid portion and metal ions (sodium ions, zinc ions, etc.); engineering plastics such as polycarbonate, polyamide, polyimide, polyetheretherketone, polyetherimide, fully aromatic polyamide, and polyphenylene sulfide; aramid (paper); glass; glass cloth; fluororesins; chlorine-based resins such as polyvinyl chloride and polyvinylidene chloride; cellulose-based resins; silicone-based resins; or mixtures of these mixed with plasticizers, or cured products crosslinked by electron beam irradiation. The base film may consist of a single base material, or it may consist of a mixed resin of two or more base materials. The base film may also be a laminated film having a laminated structure in which two or more films are laminated. From the viewpoint of controlling adhesion with the adhesive layer 3, the surface of the base film may be subjected to surface roughening treatments such as matting or corona treatment.

[0040] The adhesive layer 3 is a layer made of an adhesive. The adhesive is not particularly limited as long as it has sufficient adhesive strength to prevent the semiconductor chip from scattering in the cooling expansion process and has a low adhesive strength that does not damage the semiconductor chip in the subsequent pickup process of the semiconductor chip. Conventionally known adhesives in the field of dicing films can be used. The adhesive may be either a radiation-curable type or a non-radiation-curable type. The radiation may be, for example, ultraviolet rays. The non-radiation-curable adhesive is an adhesive that exhibits a certain adhesiveness under short-term pressure. On the other hand, the radiation-curable adhesive is an adhesive that has the property of reducing its adhesiveness upon irradiation with radiation (e.g., ultraviolet rays).

[0041] The thickness of the dicing film 4 (substrate layer 2 and adhesive layer 3) may be 60 to 150 μm or 70 to 130 μm from the viewpoints of economy and film handling properties.

[0042] The adhesive layer 1A is formed by the film-shaped adhesive 1. The film-shaped adhesive 1 may be thermosetting and may be able to reach a fully cured (C-stage) state after a curing process through a semi-cured (B-stage) state. The film-shaped adhesive 1 may be a die bonding film used for bonding a semiconductor chip to a support member or for bonding semiconductor chips to each other.

[0043] The film-shaped adhesive 1 may contain a thermosetting resin component (hereinafter sometimes referred to as the “(A) component”) and an elastomer (hereinafter sometimes referred to as the “(B) component”), and may further contain an inorganic filler (hereinafter sometimes referred to as the “(C) component”). The film-shaped adhesive 1 may not contain the (C) component. The (A) component may include, for example, an epoxy resin (hereinafter sometimes referred to as the “(A1) component”) and a phenolic resin (hereinafter sometimes referred to as the “(A2) component”). In addition to the (A) component, the (B) component, and the (C) component, the film-shaped adhesive 1 may further contain a coupling agent (hereinafter sometimes referred to as the “(D) component”), a curing accelerator (hereinafter sometimes referred to as the “(E) component”), and other components, etc.

[0044] (A) component: thermosetting resin component; (A1) component: epoxy resin. Component (A1) can be used without particular limitations as long as it has an epoxy group in its molecule. Examples of component (A1) include bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; phenol novolac type epoxy resin; cresol novolac type epoxy resin; bisphenol A novolac type epoxy resin; bisphenol F novolac type epoxy resin; stilbene type epoxy resin; triazine skeleton-containing epoxy resin; fluorene skeleton-containing epoxy resin; triphenolmethane type epoxy resin; biphenyl type epoxy resin; xylylene type epoxy resin; biphenyl aralkyl type epoxy resin; naphthalene type epoxy resin; and diglycidyl ether compounds of polycyclic aromatics such as polyfunctional phenols and anthracenes. Among these, component (A1) may include cresol novolac type epoxy resin, bisphenol F type epoxy resin, or bisphenol A type epoxy resin from the viewpoint of the film's tackiness, flexibility, etc. Bisphenol F type epoxy resins, for example, often have a relatively low softening point, with many having a softening point of 40°C or below.

[0045] Component (A1) may include a liquid epoxy resin (hereinafter sometimes referred to as "component (A1a)") having a softening point of 40°C or lower (for example, being liquid at 30°C). Component (A1) may be a combination of component (A1a) and a solid epoxy resin (hereinafter sometimes referred to as "component (A1b)") having a softening point exceeding 40°C (for example, being solid at 30°C). Component (A1) tends to more easily improve the storage modulus after curing by including component (A1a). Furthermore, component (A1) being a combination of component (A1a) and component (A1b) tends to make it easier to achieve thin films.

[0046] The softening point of component (A1) can be measured, for example, by the ring-sphere method in accordance with JIS K7234:1986. Alternatively, the softening point of component (A1) may be taken from, for example, the manufacturer's catalog value.

[0047] Examples of commercially available products of component (A1a) include EXA-830CRP (product name, manufactured by DIC Corporation, liquid at 30°C), YDF-8170C (product name, manufactured by Nippon Steel Chemical & Material Co., Ltd., liquid at 30°C), and EP-4088S (product name, manufactured by ADEKA Corporation, liquid at 30°C).

[0048] Examples of commercially available components of (A1b) include YDCN-700-10 (product name, manufactured by Nippon Steel Chemical & Material Co., Ltd., cresol novolac type epoxy resin, epoxy equivalent: 210 g / eq, softening point: 80°C), N-500P-10 (product name, manufactured by DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent: 204 g / eq, softening point: 84°C), HP-4710 (product name, manufactured by DIC Corporation, naphthalene type epoxy resin, epoxy equivalent: 170 g / eq, softening point: 95°C), and NC-7000L (product name, manufactured by Nippon Kayaku Co., Ltd., naphthalene type epoxy resin, epoxy equivalent: 230 g / eq, softening point: 88°C).

[0049] When component (A1) is a combination of component (A1a) and component (A1b), the content of component (A1a) may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, and may be 60% by mass or less, 50% by mass or less, or 40% by mass or less, based on the total amount of component (A1). The content of component (A1a) in component (A1) in the adhesive composition when forming a film-like adhesive may be the same as the above range.

[0050] When component (A1) is a combination of component (A1a) and component (A1b), the content of component (A1b) may be 40% by mass or more, 50% by mass or more, or 60% by mass or more, and may be 99% by mass or less, 97% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less, based on the total amount of component (A1). The content of component (A1b) in component (A1) in the adhesive composition when forming a film-like adhesive may be the same as the above range.

[0051] The epoxy equivalent of component (A1) is not particularly limited, but may be 80 to 350 g / eq or 100 to 300 g / eq. When the epoxy equivalent of component (A1) is within this range, it tends to be easier to maintain the bulk strength of the film-like adhesive while ensuring the fluidity of the adhesive composition when forming the film-like adhesive. The epoxy equivalent of component (A1) can be measured, for example, by potentiometric titration in accordance with JIS K7236:2009. Alternatively, the epoxy equivalent of component (A1) may be taken from, for example, the catalog value of the supplier.

[0052] • Component (A2): Phenolic resin. Component (A2) acts as a curing agent for component (A1), i.e., it can be a curing agent for epoxy resin. By containing component (A2) in the film adhesive, the film adhesive can be crosslinked at high density, improving the storage modulus after curing.

[0053] Component (A2) can be used without particular limitations as long as it has a phenolic hydroxyl group in its molecule. Examples of component (A2) include novolac-type phenolic resins obtained by condensing or co-condensing phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde under an acidic catalyst; phenolic aralkyl resins synthesized from phenols such as allylated bisphenol A, allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenol and / or naphthols with dimethoxyp-xylene or bis(methoxymethyl)biphenyl; naphthol aralkyl resins; biphenyl aralkyl-type phenolic resins; and phenyl aralkyl-type phenolic resins. Among these, component (A2) may include novolac-type phenolic resin or phenyl aralkyl-type phenolic resin.

[0054] The hydroxyl group equivalent of component (A2) may be 70 to 300 g / eq or 90 to 280 g / eq. When the hydroxyl group equivalent of component (A2) is 70 g / eq or more, it is possible to prevent problems caused by foaming, outgassing, etc., and when it is 300 g / eq or less, the storage modulus tends to improve further. The hydroxyl group equivalent of component (A2) can be measured by titration using, for example, the acetylation method with acetic anhydride. Alternatively, the hydroxyl group equivalent of component (A2) may be taken from, for example, the catalog value of the distributor.

[0055] (A2) The softening point of component (A2) is not particularly limited, but may be, for example, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, or 110°C or higher. The upper limit of the softening point of component (A2) may be, for example, 200°C or lower. The softening point of component (A2) can be measured, for example, by the ring-and-ball method in accordance with JIS K6910:2007. The softening point of component (A2) may be, for example, the value in the manufacturer's catalog.

[0056] (A2) Examples of commercially available components include MEH-7800M (trade name, manufactured by Meiwa Kasei Co., Ltd. (now UBE Co., Ltd.), phenylaralkyl type phenolic resin, hydroxyl group equivalent: 174 g / eq, softening point: 82°C), PSM-4326 (trade name, manufactured by Gun-ei Chemical Industry Co., Ltd., softening point: 120°C), J-DPP-140 (trade name, manufactured by JFE Chemical Corporation, softening point: 140°C), and GPH-103 (trade name, manufactured by Nippon Kayaku Co., Ltd., softening point: 103°C).

[0057] The equivalent ratio (epoxy groups / hydroxyl groups) of the number of epoxy groups in component (A1) to the number of hydroxyl groups in component (A2) may be 0.30 / 0.70 to 0.70 / 0.30, 0.35 / 0.65 to 0.65 / 0.35, 0.40 / 0.60 to 0.60 / 0.40, or 0.45 / 0.55 to 0.55 / 0.45 from the viewpoint of curability. When the equivalent ratio is 0.30 / 0.70 or higher, more sufficient curability tends to be obtained. When the equivalent ratio is 0.70 / 0.30 or lower, it is possible to prevent the viscosity from becoming too high and to obtain more sufficient fluidity.

[0058] The content of component (A1) (the sum of components (A1a) and (A1b)) may be 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more, based on the total amount of the film-like adhesive. When the content of component (A1) is within this range, it tends to be easier to improve the storage modulus after curing. From the viewpoint of handling, the content of component (A1) may be 60% by mass or less, 55% by mass or less, 50% by mass or less, or 45% by mass or less, based on the total amount of the film-like adhesive. The content of component (A1) (the sum of components (A1a) and (A1b)) in the adhesive composition when forming the film-like adhesive may be the same as the above range. The total amount of the film-like adhesive can be replaced with the total amount of the adhesive layer. The same applies below to the content based on the total amount of the film-like adhesive.

[0059] The content of component (A2) may be 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, based on the total amount of the film-like adhesive. When the content of component (A2) is within this range, it tends to be easier to improve the storage modulus after curing. From the viewpoint of handling, the content of component (A2) may be 40% by mass or less, 35% by mass or less, or 30% by mass or less, based on the total amount of the film-like adhesive. The content of component (A2) in the adhesive composition when forming the film-like adhesive may be the same as the above range.

[0060] The content of component (A) (the sum of components (A1) and (A2)) may be 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total amount of the film-like adhesive. When the content of component (A) is within this range, it tends to be easier to improve the storage modulus after curing. From the viewpoint of handling, the content of component (A) may be 80% by mass or less, 75% by mass or less, or 70% by mass or less, based on the total amount of the film-like adhesive. The content of component (A) (the sum of components (A1) and (A2)) in the adhesive composition when forming the film-like adhesive may be the same as the above range.

[0061] Component (B): Elastomer Component (B) is an elastomer (a resin with rubber-like elasticity). Component (B) is a (meth)acrylate polymer containing structural units derived from (meth)acrylate having epoxy groups, which is extremely good at cooling and discontinuing, has fewer ionic impurities and therefore has superior heat resistance, makes it easier to ensure connection reliability of semiconductor devices, and has excellent fluidity, and is a (meth)acrylate polymer (hereinafter sometimes referred to as "component (B1)") that satisfies at least one of conditions A, B, and C. By including component (B1) in component (B), the crosslinking density after curing tends to improve dramatically, suppressing chip cracks during wire bonding (i.e., excellent wire bonding properties) and improving processability during film cutting (for example, film cutting properties for circular die-cutting). Component (B1) may satisfy at least two of conditions A, B, and C, or it may satisfy all of conditions A, B, and C.

[0062] Component (B1) is a (meth)acrylate polymer containing structural units derived from (meth)acrylate having an epoxy group. Examples of compounds that provide structural units derived from (meth)acrylate having an epoxy group include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, the compound that provides structural units derived from (meth)acrylate having an epoxy group may be glycidyl (meth)acrylate or glycidyl methacrylate.

[0063] (Condition A) The content of structural units derived from (meth)acrylate having epoxy groups is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer. When the content of structural units derived from (meth)acrylate having epoxy groups is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer, it is possible to impart good processability and excellent wire bonding properties when applied to a film-like adhesive. The content of structural units derived from (meth)acrylate having epoxy groups may be 8% by mass or more, 10% by mass or more, 12% by mass or more, 14% by mass or more, 16% by mass or more, 18% by mass or more, 20% by mass or more, or 22% by mass or more, based on the total structural units of the (meth)acrylate polymer, and may be 30% by mass or less, 28% by mass or less, 26% by mass or less, 24% by mass or less, 22% by mass or less, 20% by mass or less, 18% by mass or less, 16% by mass or less, or 14% by mass or less.

[0064] In this specification, the content of each structural unit in a polymer refers to the ratio of the charged mass of the monomer corresponding to each structural unit to the total amount of monomers used in polymerization. The content of structural units derived from (meth)acrylate having an epoxy group can be calculated, for example, from the amount of monomer used in the production of the (meth)acrylate polymer.

[0065] (Condition B) The epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or higher. When the epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or higher, it is possible to impart good processability and excellent wire bonding properties when applied to a film-like adhesive. The epoxy value of the (meth)acrylate polymer is 0.42 eq / kg or higher, 0.50 eq / kg or higher, 0.55 eq / kg or higher, 0.60 eq / kg or higher, 0.65 eq / kg or higher, 0.70 eq / kg or higher, 0.75 eq / kg or higher, 0.80 eq / kg or higher, 0.85 eq / kg or higher, 0.90 eq / kg or higher, and 0.95 eq / kg, based on the total structural units of the (meth)acrylate polymer. It may be g or more, 1.00 eq / kg or more, 1.05 eq / kg or more, or 1.10 eq / kg or more, and may be 2.00 eq / kg or less, 1.80 eq / kg or less, 1.60 eq / kg or less, 1.40 eq / kg or less, 1.20 eq / kg or less, 1.10 eq / kg or less, 1.00 eq / kg or less, 0.90 eq / kg or less, 0.80 eq / kg or less, or 0.70 eq / kg or less.

[0066] In this specification, epoxy value (epoxy index) refers to the number of equivalent epoxy groups contained in 1 kg of (meth)acrylate polymer. The epoxy value (epoxy index) is a value measured by indicator titration in accordance with JIS K7236:2009.

[0067] (Condition C) In the infrared absorption spectrum of a (meth)acrylate polymer, when P(A) is the area of ​​the absorption peak originating from the antisymmetric stretching of the epoxy group and P(B) is the area of ​​the absorption peak originating from the stretching vibration of the carbonyl group, P(A) and P(B) satisfy the condition of the following formula (1): P(A) / P(B) ≥ 0.0055 (1)

[0068] The P(A) / P(B) ratio is 0.0055 or higher. When P(A) / P(B) is 0.0055 or higher, it is possible to provide good processability and excellent wire bonding properties when applied to a film-type adhesive. P(A) / P(B) may be 0.0060 or greater, 0.0070 or greater, 0.0080 or greater, 0.0090 or greater, 0.0100 or greater, 0.0120 or greater, 0.0140 or greater, 0.0160 or greater, 0.0180 or greater, 0.0200 or greater, or 0.0220 or greater, and may be 0.0500 or less, 0.0450 or less, 0.0420 or less, 0.0400 or less, 0.0350 or less, 0.0300 or less, 0.0280 or less, 0.0260 or less, 0.0240 or less, 0.0220 or less, 0.0200 or less, 0.0180 or less, 0.0160 or less, 0.0140 or less, 0.0120 or less, or 0.0110 or less.

[0069] The epoxy group mainly originates from (meth)acrylate having the epoxy group as its structural unit, and the carbonyl group mainly originates from (meth)acrylate having the epoxy group as its structural unit. That is, P(A) / P(B) represents the ratio of (meth)acrylate having the epoxy group to the total amount of (meth)acrylate in the (meth)acrylate polymer. The area of ​​the absorption peak (P(A)) due to the antisymmetric stretching of the epoxy group and the area of ​​the absorption peak (P(B)) due to the stretching vibration of the carbonyl group can be calculated, for example, by the following method.

[0070] First, the total internal reflection (IR) spectrum of the (meth)acrylate polymer is obtained using the ATR method (total internal reflection measurement). For IR measurement, for example, a LUMOS II (Bruker, ATR crystal: germanium, detector: MCT, infrared incidence angle: 30°) can be used. The IR measurement for the (meth)acrylate polymer is performed after background measurement, and the obtained spectrum is corrected for atmospheric pressure. Next, the vertical axis is set to absorbance and the horizontal axis to wavenumber (cm²). －１ Display the spectrum using ), and in the displayed spectrum, 880 cm －１ and 927 cm －１Determine the wavenumbers of two points corresponding to the minimum absorbance within the specified range. The straight line connecting these two points on the spectrum is defined as the baseline. The area of ​​absorbance enclosed by the spectrum and the baseline is defined as the area of ​​the absorption peak (P(A)) originating from the antisymmetric stretching of the epoxy group. (1661 cm⁻¹ on the spectrum) －１ and 1842 cm －１ The straight line connecting these two points is defined as the baseline, and the area of ​​absorbance enclosed by the spectrum and the baseline is defined as the area of ​​the absorption peak originating from the stretching vibration of the carbonyl group (P(B)). Based on P(A) and P(B) defined in this way, P(A) / P(B) can be calculated.

[0071] The epoxy value under condition B and the P(A) / P(B) under condition C can also be determined by extracting the (meth)acrylate polymer from the film-like adhesive described below and obtaining the extracted (meth)acrylate polymer. Methods for extracting the (meth)acrylate polymer from the film-like adhesive include, for example, Method 1 and Method 2. ・Method 1 (When the film-like adhesive is completely soluble in tetrahydrofuran (THF)) The film-like adhesive is dissolved in THF, and the (meth)acrylate polymer is separated and recovered based on molecular size (molecular weight) by preparative gel permeation chromatography (preparative GPC). ・Method 2 (When the film-like adhesive is not completely soluble in tetrahydrofuran (THF)) The film-like adhesive is thoroughly washed with acetonitrile to elute components other than the (meth)acrylate polymer from the film-like adhesive, and the (meth)acrylate polymer is recovered.

[0072] The (meth)acrylate polymer may further contain structural units derived from (meth)acrylates other than those having epoxy groups, in addition to structural units derived from (meth)acrylates having epoxy groups.

[0073] Other compounds that provide structural units derived from (meth)acrylate may be (meth)acrylates having one (meth)acryloyl group. Examples of other (meth)acrylates include (meth)acrylic acid; (meth)acrylamide; (meth)acryloylmorpholine; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Alkyl (meth)acrylates having alkyl groups with 1 to 18 carbon atoms, such as isodecyl (meth)acrylate, dodecyl (meth)acrylate (n-lauryl (meth)acrylate), isomiristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; alkenyl (meth)acrylates having alkenyl groups with 2 to 18 carbon atoms, such as 3-butenyl (meth)acrylate; aromatic rings such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate (Meth)acrylates having alicyclic groups; methoxytetraethylene glycol (meth)acrylate, methoxyhexaethylene glycol (meth)acrylate, methoxyoctaethylene glycol (meth)acrylate, methoxynononaethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxyheptapropylene glycol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, etc.; (meth)acrylates having alicyclic groups such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; (meth)acrylates having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate;Examples include (meth)acrylamide derivatives such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and N-hydroxyethyl (meth)acrylamide; (meth)acrylonitriles such as acrylonitrile and methacrylonitrile; polyalkylene glycol mono(meth)acrylates such as tetraethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, octapropylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, and tripropylene glycol mono(meth)acrylate; and (meth)acrylates having a siloxane skeleton. Among these, other (meth)acrylates may include at least one selected from the group consisting of alkyl (meth)acrylates and (meth)acrylonitriles. The alkyl (meth)acrylate may be an alkyl (meth)acrylate having an alkyl group with 1 to 6 carbon atoms. The (meth)acrylonitrile may be acrylonitrile.

[0074] The content of other structural units derived from (meth)acrylate may be 70% by mass or more, 72% by mass or more, 74% by mass or more, 76% by mass or more, 78% by mass or more, 80% by mass or more, 82% by mass or more, 84% by mass or more, or 86% by mass or more, based on the total structural units of the (meth)acrylate polymer, and may be 94% by mass or less, 92% by mass or less, 90% by mass or less, 88% by mass or less, 86% by mass or less, 84% by mass or less, 82% by mass or less, 80% by mass or less, or 78% by mass or less.

[0075] The (meth)acrylate polymer may further contain structural units derived from copolymer monomers copolymerizable with (meth)acrylate, in addition to structural units derived from epoxy group-containing (meth)acrylate and other structural units derived from (meth)acrylate. Examples of compounds that provide structural units derived from copolymer monomers include styrene, 4-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, cyclohexylmaleimide, phenylmaleimide, and maleic anhydride. The content of copolymer monomers may be 0 to 30% by mass, 0 to 20% by mass, 0 to 10% by mass, or 0 to 5% by mass, based on the total structural units of the (meth)acrylate polymer.

[0076] In one embodiment, the (meth)acrylate polymer may contain structural units derived from epoxy group-containing (meth)acrylate, structural units derived from alkyl (meth)acrylate, and structural units derived from (meth)acrylonitrile. In one embodiment, the (meth)acrylate polymer may be composed of these structural units.

[0077] The weight-average molecular weight (Mw) of the (meth)acrylate polymer may be between 200,000 and 2,000,000. When the weight-average molecular weight (Mw) of the (meth)acrylate polymer is within this range, the effects of this disclosure tend to be more easily obtained, allowing for appropriate control of film formation properties, film strength, flexibility, tackiness, etc., as well as excellent reflowability and improved embedding properties. The weight-average molecular weight (Mw) of the (meth)acrylate polymer may be 300,000 or more, 400,000 or more, 500,000 or more, or 550,000 or more, and may be 1,800,000 or less, 1,500,000 or less, 1,300,000 or less, or 1,100,000 or less.

[0078] In this specification, weight-average molecular weight (Mw) refers to the value obtained by measuring by gel permeation chromatography (GPC) and converting it using a calibration curve with standard polystyrene. If multiple peaks are observed in the GPC, the weight-average molecular weight attributable to the peak with the highest intensity is defined as the weight-average molecular weight in this specification.

[0079] (Meth)acrylate polymers can be obtained by known methods of synthesis. Examples of synthesis methods include solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, precipitation polymerization, gas-phase polymerization, plasma polymerization, and supercritical polymerization. Examples of polymerization reactions include radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization (ATRP (atomic transfer radical polymerization), RAFT (reversible addition-cleavage chain transfer polymerization), etc.), living cationic polymerization, living anionic polymerization, coordination polymerization, and immortal polymerization. Among these, synthesis by radical polymerization using solution polymerization has advantages such as cost-effectiveness, high reaction rate, ease of polymerization control, and the ability to directly use the resin solution obtained by polymerization in formulations.

[0080] Here, we will describe a method for producing (meth)acrylate polymers by radical polymerization using solution polymerization.

[0081] In one embodiment, a (meth)acrylate polymer can be obtained by a method comprising the step of polymerizing an epoxy group-containing (meth)acrylate and, optionally, a monomer containing other (meth)acrylates and copolymer monomers.

[0082] To obtain such (meth)acrylate polymers, known radical polymerization initiators can be used. Examples of radical polymerization initiators include azo polymerization initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis(2,4,4-trimethylpentane), and dimethyl-2,2'-azobis(2-methylpropionate); and peroxide polymerization initiators such as benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and 1,1-bis(t-butylperoxy)cyclododecane.

[0083] The amount of radical polymerization initiator used may be 0.01 to 5 parts by mass, 0.02 to 4 parts by mass, or 0.03 to 3 parts by mass per 100 parts by mass of the total monomers.

[0084] The solvent used in solution polymerization is not particularly limited as long as it is a solvent capable of dissolving the (meth)acrylate polymer. Examples of solvents include known organic solvents such as esters like ethyl acetate, propyl acetate, and butyl acetate; aromatic hydrocarbons like toluene, xylene, and benzene; aliphatic hydrocarbons like hexane and heptane; alicyclic hydrocarbons like cyclohexane and methylcyclohexane; ketones like methyl ethyl ketone and methyl isobutyl ketone; glycols like ethylene glycol, propylene glycol, and dipropylene glycol; glycol ethers like methyl cellosolve, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; and glycol esters like ethylene glycol diacetate and propylene glycol monomethyl ether acetate. Furthermore, polymerization can also be carried out using supercritical carbon dioxide or the like as a solvent.

[0085] The reaction temperature can be set appropriately depending on the type of radical polymerization initiator used. For example, the reaction temperature may be 40 to 125°C or 60 to 120°C. The reaction time can also be set appropriately depending on the type of radical polymerization initiator used. For example, the reaction time may be 1 to 24 hours or 3 to 15 hours.

[0086] Component (B) may further contain, in addition to component (B1), an elastomer other than component (B1) (hereinafter sometimes referred to as "component (B2)"). Examples of component (B2) include (meth)acrylate polymers other than component (B1) (including (meth)acrylic rubber), urethane resins (including urethane rubber), silicone resins (including silicone rubber), styrene-based elastomers, etc.

[0087] The weight-average molecular weight (Mw) of component (B2) may be 100,000 or more, 300,000 or more, or 500,000 or more, and may be 3,000,000 or less, 2,000,000 or less, or 1,000,000 or less.

[0088] The content of component (B1) may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, or 100% by mass, based on the total amount of component (B). The content of component (B1) in component (B) in the adhesive composition when forming a film-like adhesive may be the same as the above range.

[0089] The content of component (B2) may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, or 5% by mass or less, based on the total amount of component (B), and may also be 0% by mass. The content of component (B2) in component (B) in the adhesive composition when forming a film-like adhesive may be the same as the above range.

[0090] The content of component (B) may be 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 42% by mass or more, or 45% by mass or more, based on the total amount of the film-like adhesive. When the content of component (B) is within this range, it tends to exhibit excellent thin-film formation properties, excellent elongation at break when a thin film is formed, and suppress warping of semiconductor devices (semiconductor packages). When the content of component (B) is 40% by mass or more, based on the total amount of the film-like adhesive, the flexibility of the film is optimized, the elongation at break when a thin film of 15 μm or less is improved, and the warping of semiconductor devices (semiconductor packages) after lamination tends to be suppressed. The content of component (B) may be 60% by mass or less, 55% by mass or less, 50% by mass or less, or 45% by mass or less, based on the total amount of the film-like adhesive. When the content of component (B) is within this range, it tends to be easier to further improve the storage modulus after curing. The content of component (B) in the adhesive composition when forming the film-like adhesive may be the same as the range described above.

[0091] (C) Component: The inorganic filler film adhesive 1 may further contain component (C), or it may not contain component (C). In other words, the film adhesive 1 may exist in an embodiment that contains component (C) and an embodiment that substantially does not contain component (C).

[0092] Examples of component (C) include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, and silica. Among these, component (C) may be silica from the viewpoint of adjusting the melt viscosity. The shape of component (C) is not particularly limited, but it may be spherical.

[0093] The average particle size of component (C) may be 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less, from the viewpoint of fluidity and storage modulus. The average particle size of component (C) may be, for example, 0.01 μm or more. Here, the average particle size refers to the particle size with an integrated frequency of 50% in the particle size distribution determined by the laser diffraction / scattering method. The average particle size of component (C) can also be determined by using a film-like adhesive containing component (C). In this case, the residue obtained by heating the film-like adhesive to decompose the resin component is dispersed in a solvent to prepare a dispersion, and the average particle size of component (C) can be determined from the particle size distribution obtained by applying the laser diffraction / scattering method to this dispersion.

[0094] The content of component (C) may be 0 to 5% by mass based on the total amount of the film-like adhesive. When the content of component (C) is within this range, it tends to be possible to further thin films. Also, when the content of component (C) is within this range, the elongation at break when a thin film is formed is excellent, the processability is excellent, and the warping of semiconductor devices (semiconductor packages) tends to be suppressed. In one embodiment, the content of component (C) may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, or 0.1% by mass or less, based on the total amount of the film-like adhesive. In one embodiment, the content of component (C) may be 0% by mass based on the total amount of the film-like adhesive. That is, in one embodiment, the film-like adhesive may not contain component (C). In one embodiment, the content of component (C) may be 0% by mass or more, greater than 0% by mass, or 1% by mass or more, based on the total amount of the film-like adhesive. Furthermore, the content of component (C) in the adhesive composition when forming the film-like adhesive may be the same as the range described above.

[0095] Component (A) and component (B), or component (A), component (B), and component (C) may be the main components of the film-like adhesive of this embodiment. The total content of component (A) and component (B), or the total content of component (A), component (B), and component (C), may be, for example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 96% by mass or more, 97% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.7% by mass or more, or 99.9% by mass or more, based on the total amount of the film-like adhesive. The total content of component (A) and component (B), or the total content of component (A), component (B), and component (C), may be, for example, 100% by mass or less, 99.9% by mass or less, 99.7% by mass or less, or 99.5% by mass or less, based on the total amount of the film-like adhesive.

[0096] (D) Component: Coupling agent Component (D) may be a silane coupling agent. Examples of silane coupling agents include γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane.

[0097] (E) component: curing accelerator. Examples of (E) component include imidazoles and their derivatives, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, etc. Among these, from the viewpoint of reactivity, (E) may be imidazoles and their derivatives.

[0098] Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole.

[0099] Component (E) may contain 2-phenylimidazole because it readily promotes hardening at low temperatures.

[0100] The film-like adhesive may further contain other components. Examples of other components include pigments, ion capture agents, antioxidants, and so on.

[0101] The total content of component (D), component (E), and other components may be 0% by mass or more, 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, based on the total amount of the film-like adhesive, and may be 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less. The total content of component (D), component (E), and other components in the adhesive composition when forming the film-like adhesive may be the same as the above range.

[0102] The thickness of the film-like adhesive 1 (adhesive layer 1A) may be 15 μm or less. The thickness of the film-like adhesive 1 may be 12 μm or less, 10 μm or less, 8 μm or less, 6 μm or less, 4 μm or less, or 3 μm or less. The thickness of the film-like adhesive 1 may be, for example, 1 μm or more. The thickness of the film-like adhesive 1 can be determined, for example, by measuring the thickness at five arbitrary locations on a cross-section of the film-like adhesive 1 using a scanning electron microscope (SEM) image and calculating the average of the measured values.

[0103] The film-like adhesive 1 (adhesive layer 1A) may be a film-like adhesive in which the fracture coefficient m obtained by a fracture evaluation method comprising the steps of: preparing the following sample from the film-like adhesive 1; performing a fracture test on the following measurement area of ​​the sample using the following indentation plate under the following conditions to determine the work of fracture W (unit: N・mm), the fracture strength P (unit: N), and the length L (unit: mm) of the sample when the sample fractures; and determining the fracture coefficient m (unit: dimensionless) expressed by formula (X) based on the work of fracture W, fracture strength P, and length L, is greater than 0 and less than or equal to 40. m = [W / (P × L)] × 1000 (X) (Sample) Width: 5 mm Length: 30 mm Thickness: 0.005 mm (Indentation plate) Thickness: 1 mm Width: 15 mm Length: 70 mm Plate angle: 45° Radius of curvature of tip: 10 μm (Measurement area) Measurement target area in the sample: 5 mm wide and 3 mm long area of ​​the sample (Conditions for cleavage test) Speed ​​mode: Constant control Test speed: 10 mm / min Test temperature: -2°C

[0104] The fracture test is described below. The fracture test is classified as a flexural strength test. This test involves pressing the center of the sample until it breaks, while both ends of the sample are fixed. Figure 5 is a schematic perspective view showing the state in which the pressing plate 25 has descended toward the sample S fixed to the frame plate 24. The sample S is subjected to the fracture test while attached to the surface of the frame plate 24. The testing machine includes members 30, 30 that hold the pressing plate 25, and a mechanism (not shown) that moves the pressing plate 25 vertically via the members 30, 30.

[0105] The frame plate 24 is made of, for example, a resin material having sufficient strength, and has a slit 24a formed in the center. For example, if the length (or width) of the measurement target portion SR in the sample S is 3 mm, the width of the slit 24a can be set to 3 mm. The length of the slit 24a only needs to be longer than the width of the press plate 25. For example, if the width of the press plate 25 is 15 mm, the length of the slit 24a can be 20 to 40 mm.

[0106] The indentation plate 25 has one end 26 that is pointed (see Figures 6(a) and 6(b)). The end 26 is composed of two surfaces 26a and 26b, and the angle between these surfaces 26a and 26b (θ in Figure 6(b)) is, for example, 30 to 60°, or it may be 35 to 50°. The radius of curvature of the tip 26c of the end 26 is, for example, 3 to 100 μm, or it may be 5 to 20 μm. The thickness of the indentation plate 25 should be sufficiently thinner than the width of the slit 24a, for example, 0.3 to 2 mm, or it may be 0.5 to 1.5 mm. On both sides of the indentation plate 25, protrusions 27, 27 are formed. The indentation plate 25 is fixed to the members 30, 30 of the testing machine via these protrusions 27, 27.

[0107] The sample S is attached to the surface 24b of the frame plate 24, for example, by double-sided adhesive tapes 28, 28 (see Figure 5). The sample S should be attached to the frame plate 24 such that its longitudinal direction is perpendicular to the longitudinal direction of the slit 24a and the center of the sample S crosses the center of the slit 24a. The measurement target portion SR in the sample S can be said to be the region corresponding to the slit 24a. The double-sided adhesive tapes 28, 28 should be positioned along the periphery of the slit 24a.

[0108] The sample S may be a piece cut from the film-like adhesive to be evaluated, and it is not necessary to prepare the sample by laminating multiple adhesive pieces cut from the film-like adhesive. In other words, the thickness of the sample S may be the same as the thickness of the film-like adhesive. The width of the sample S may be, for example, 1 to 30 mm or 3 to 8 mm. It should be set to an appropriate width depending on the condition of the measuring device. The length of the measurement target portion SR in the sample S (width of the slit 24a) may be, for example, 1 to 20 mm or 2 to 10 mm. The shape of the frame plate 24 and the size of the sample S may be other than those described above, as long as the cleavage test can be performed.

[0109] The relative speed between the indentation plate 25 and the sample S is, for example, 1 to 100 mm / min, and may also be 5 to 20 mm / min. If this relative speed is too fast, there is a tendency that sufficient data on the fracture process cannot be obtained, and if it is too slow, the stress tends to relax and fracture is difficult to achieve. The indentation distance of the indentation plate 25 is, for example, 1 to 50 mm, and may also be 5 to 30 mm. If the indentation distance is too short, fracture tends not to occur. It is preferable to prepare multiple samples of the film-like adhesive to be evaluated and perform fracture tests multiple times to confirm the stability of the test results.

[0110] The cleavage test is performed in a constant temperature chamber set to a predetermined temperature. The constant temperature chamber should be set to a constant temperature in the range of -15°C to 0°C (the temperature of the expected cooled expander). For example, the TLF-R3-F-W-PL-S manufactured by ITEC Corporation can be used as the constant temperature chamber. An autograph (for example, AZT-CA01 manufactured by A&D Corporation, load cell: 50N, compression mode) is used to obtain the cleavage work W (unit: N・mm), cleavage strength P (unit: N), and indentation distance d (unit: mm).

[0111] Figure 7 is a schematic cross-sectional view showing the state in which a load is applied to the sample S by the indentation plate 25. Figure 8 is a graph showing an example of the results of a fracture test. As shown in Figure 8, the fracture work W is the area enclosed when a graph is created with the load on the vertical axis and the indentation distance d until the sample S fractures on the horizontal axis. The fracture strength P is the load at which the sample S fractures. The indentation distance d is the distance the indentation plate 25 moves from when it comes into contact with the sample S until the sample S fractures. The length L of the sample S at the time of fracture can be calculated using the Pythagorean theorem from the length of the measurement target portion SR in the sample S (width of the slit 24a) and the value of the indentation distance d. For example, analysis software may be used to measure the values ​​of fracture work W (unit: N・mm), fracture strength P (unit: N), and indentation distance d (unit: mm).

[0112] From the values ​​of the cutting work W (unit: N・mm), cutting strength P (unit: N), and indentation distance d (unit: mm) obtained by the cleavage test, the cleavage coefficient m (unit: dimensionless) is determined from equation (X). m = [W / (P × L)] × 1000 (X) In equation (X), L represents the length of the sample S when the sample S is cleaved (unit: mm), and is a value calculated by the following equation (Xa). L = [(S / 2)] ２ +d ２ ] １／２ ×2 (Xa) In equation (Xa), S represents the length of the measurement target portion SR in the sample S (width of the slit 24a) (unit: mm).

[0113] According to the inventors' studies, when a cleavage test was conducted under the following conditions, it was found that film-like adhesives with a cleavage coefficient m greater than 0 and less than or equal to 40 tended to exhibit superior cleavage performance when subjected to cooling and expanding. (Sample) Width: 5 mm Length: 30 mm Thickness: 0.005 mm (Indentation plate) Thickness: 1 mm Width: 15 mm Length: 70 mm Plate angle: 45° Radius of curvature at tip: 10 μm (Measurement area) Measurement target area in the sample: Area of ​​the sample with a width of 5 mm and a length of 3 mm (Cleaavage test conditions) Speed ​​mode: Constant control Test speed: 10 mm / min Test temperature: -2°C

[0114] The cleavage coefficient m (unit: dimensionless) is greater than 0 and less than or equal to 40, and may be 37 or less, 35 or less, 32 or less, or 30 or less, and may be 5 or more, 10 or more, 15 or more, or 20 or more. The cleavage coefficient m is a parameter relating to the stretchability of the film-like adhesive under low-temperature conditions. When the cleavage coefficient m is 40 or less, excessive stretchability of the film-like adhesive is suppressed, and it tends to exhibit excellent dicing properties, especially in the cooling and expanding process in semiconductor wafer dicing methods such as the SDBG method and DBG method. Furthermore, when the cleavage coefficient m is 15 or more, it tends to exhibit good stress propagation. Film-like adhesives with a cleavage coefficient m within the above range can be suitably used for stealth dicing. Film-like adhesives with a cleavage coefficient m within the above range exhibit excellent cooling and dicing properties and can be applied to semiconductor device manufacturing processes in which cooling and expanding is performed.

[0115] The film-like adhesive 1 is formed by molding an adhesive composition containing component (A) and component (B), and optionally component (C) and additional components, into a film. Such a film-like adhesive 1 can be formed by applying the adhesive composition to a support film. In forming the film-like adhesive 1, a varnish (adhesive varnish) containing the adhesive composition and a solvent may be used. When using an adhesive varnish, the adhesive varnish can be prepared by mixing or kneading component (A) and component (B), and optionally component (C) and additional components, in a solvent, applying the obtained adhesive varnish to a support film, and removing the solvent by heating and drying to obtain the film-like adhesive 1.

[0116] The support film is not particularly limited as long as it can withstand the above-mentioned heat drying, but may be, for example, polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide film, polyethylene naphthalate film, polymethylpentene film, etc. The support film may be a multilayer film made by combining two or more types, and its surface may be treated with a release agent such as silicone or silica. The thickness of the support film may be, for example, 10 to 200 μm or 20 to 170 μm.

[0117] Mixing or kneading can be carried out using conventional agitators, dispersers, three-roll mills, ball mills, and other dispersers, in appropriate combinations.

[0118] The solvent used in the preparation of the adhesive varnish is not limited as long as it can uniformly dissolve, knead, or disperse each component, and conventionally known solvents can be used. Examples of such solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, as well as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, and xylene. From the viewpoint of drying speed and cost, the solvent may be methyl ethyl ketone or cyclohexanone.

[0119] Known methods can be used to apply the adhesive varnish to the support film, such as the knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, and curtain coating method. The heating and drying conditions are not particularly limited as long as the solvent used is sufficiently evaporated, but may be 50 to 150°C for 1 to 30 minutes.

[0120] The dicing-die bonding integrated film 10 can be obtained, for example, by preparing a film-like adhesive 1 and a dicing film 4, and bonding the film-like adhesive 1 and the adhesive layer 3 of the dicing film 4 together. Alternatively, the dicing-die bonding integrated film 10 can also be obtained, for example, by preparing a dicing film 4 and applying an adhesive composition (adhesive varnish) onto the adhesive layer 3 of the dicing film 4, similar to the method for forming the film-like adhesive 1 described above.

[0121] When bonding a film-like adhesive 1 to the adhesive layer 3 of a dicing film 4, the integrated dicing-die bonding film 10 can be formed by laminating the film-like adhesive 1 onto the dicing film 4 under predetermined conditions (for example, at room temperature (25°C) or in a heated state) using a roll laminator, vacuum laminator, etc. Since the integrated dicing-die bonding film 10 can be manufactured continuously and is highly efficient, it may also be formed using a roll laminator in a heated state.

[0122] The present disclosure will be described below in detail based on examples, but the present disclosure is not limited to these examples.

[0123] [Synthesis of (meth)acrylate polymers] <Production Example 1> Butyl acrylate (BA), ethyl acrylate (EA), glycidyl methacrylate (GMA), and acrylonitrile (AN) were prepared as monomers. The content of glycidyl methacrylate was adjusted to 11.0% by mass based on the total amount of monomers, and these monomers were polymerized using a solution polymerization method to obtain a solution containing the (meth)acrylate polymer of Production Example 1.

[0124] <Production Example 2> Using the same monomers as in Production Example 1, except that the glycidyl methacrylate content was adjusted to 16.8% by mass based on the total amount of monomers, a solution containing the (meth)acrylate polymer of Production Example 2 was obtained by adjusting the ratio of other monomers and / or polymerization conditions.

[0125] <Production Example 3> Using the same monomers as in Production Example 1, except that the glycidyl methacrylate content was adjusted to 22.2% by mass based on the total amount of monomers, and adjusting the ratio of other monomers and / or polymerization conditions, a solution containing the (meth)acrylate polymer of Production Example 3 was obtained.

[0126] [Evaluation of (meth)acrylate polymers] (Measurement of weight-average molecular weight (Mw)) As a sample for Mw measurement, a solution containing (meth)acrylate polymer was dissolved in tetrahydrofuran (THF) to prepare a 0.2 mass% THF solution. Mw was measured by gel permeation chromatography (GPC) and derived by conversion using a calibration curve for standard polystyrene. The GPC conditions are shown below. The results are shown in Table 1. Measuring device: SHOWDEX® GPC-101 (manufactured by RESONAC Corporation) Detector: Differential refractometer SHOWDEX RI-71S (manufactured by RESONAC Corporation) Column: SHOWDEX LF-804 + LF-804 (manufactured by RESONAC Corporation) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1 mL / min

[0127] (Measurement of epoxy value (epoxy index)) The epoxy value (epoxy index) was measured by indicator titration in accordance with JIS K7236:2009. The results are shown in Table 1.

[0128] (Calculation of P(A) / P(B)) For the (meth)acrylate polymer, an IR spectrum was obtained and P(A) / P(B) was calculated. First, for the (meth)acrylate polymer, a total reflection IR spectrum was obtained by the ATR method (total reflection measurement method). For the IR measurement, LUMOS II (manufactured by Bruker, ATR crystal: germanium, detector: MCT, infrared incident angle: 30°) was used. The IR measurement of the (meth)acrylate polymer was performed after the background measurement, and the obtained spectrum was subjected to atmospheric correction. Next, the spectrum was displayed with the absorbance on the vertical axis and the wave number (cm －１ ), and in the displayed spectrum, the wave numbers of two points corresponding to the minimum values of the absorbance in the range of 880 cm －１ and 927 cm －１ were determined. A straight line connecting the two points of the wave numbers on the spectrum was used as the baseline, and the area of the absorbance surrounded by the spectrum and the baseline was calculated as the area of the absorption peak (P(A)) derived from the antisymmetric stretching of the epoxy group. A straight line connecting the two points of 1661 cm －１ and 1842 cm －１ on the spectrum was used as the baseline, and the area of the absorbance surrounded by the spectrum and the baseline was calculated as the area of the absorption peak (P(B)) derived from the stretching vibration of the carbonyl group. Based on the calculated P(A) and P(B), P(A) / P(B) was determined. The results are shown in Table 1.

[0129]

[0130] [Preparation of Film状 Adhesive] <Examples 1 to 3 and Comparative Example 1> (Preparation of Adhesive Varnish) By using each component shown in Table 2 at each content (unit: part by mass) shown in Table 2, the adhesive varnishes of Examples 1 to 3 and Comparative Example 1 were prepared. Specifically, cyclohexanone was added to a mixture composed of component (A) (components (A1) and (A2)) and, if necessary, component (C), and the mixture was stirred and mixed. Component (B) was added thereto and stirred, and further components (D) and (E) were added, and the mixture was stirred until each component became uniform to obtain the adhesive varnishes of Examples 1 to 3 and Comparative Example 1. Each component shown in Table 2 means the following, and the numerical values shown in Table 2 mean the parts by mass of the components (solid content) excluding solvents and the like.

[0131] (A) Component: Thermosetting resin component, (A1) Component: Epoxy resin (A1a-1) EXA-830CRP (Trade name, manufactured by DIC Corporation, Bisphenol F type epoxy resin, Epoxy equivalent: 155-163 g / eq, Softening point: Below 40°C, Liquid at 30°C) (A1b-1) N-500P-10 (Trade name, manufactured by DIC Corporation, o-Cresol novolac type epoxy resin, Epoxy equivalent: 204 g / eq, Softening point: 84°C, Solid at 30°C) (A1b-2) HP-4710 (Trade name, manufactured by DIC Corporation, Naphthalene type epoxy resin, Epoxy equivalent: 170 g / eq, Softening point: 95°C, Solid at 30°C)

[0132] • (A2) Ingredients: Phenolic resin (A2-1) PSM-4326 (product name, manufactured by Gun-ei Chemical Industry Co., Ltd., novolac-type phenolic resin, hydroxyl group equivalent: 105 g / eq, softening point: 120°C)

[0133] (B) Component: Elastomer, (B1) Component: (meth)acrylate polymer (B1-1) (meth)acrylate polymer from Production Example 1 (weight-average molecular weight: 850,000, GMA content (based on total monomer amount): 11.0% by mass, epoxy value: 0.55 eq / kg, P(A) / P(B): 0.0100) (B1-2) (meth)acrylate polymer from Production Example 2 (weight-average molecular weight: 650,000, GMA content (based on total monomer amount): 16.8% by mass, epoxy value: 0.84 eq / kg, P(A) / P(B): 0.0169) (B1-3) (meth)acrylate polymer of Production Example 3 (weight average molecular weight: 600,000, GMA content (based on total monomer amount): 22.2% by mass, epoxy value: 1.11 eq / kg, P(A) / P(B): 0.0249) ・(B2) component: elastomer other than component (B1) (B2-1) SG-P3 (product name, manufactured by Nagase ChemteX Corporation, (meth)acrylate polymer of butyl acrylate (BA) / ethyl acrylate (EA) / glycidyl methacrylate (GMA) / acrylonitrile (AN), weight average molecular weight: 800,000, GMA content (based on total monomer amount): 3.0% by mass, epoxy value: 0.15 eq / kg, P(A) / P(B): 0.0028)

[0134] (D) Ingredients: Coupling agent (D-1) Z-6119 (Trade name, manufactured by Dow Toray Corporation, γ-ureidopropyltriethoxysilane) (D-2) A-189 (Trade name, manufactured by Momentive Performance Materials Japan LLC, γ-mercaptopropyltrimethoxysilane)

[0135] (E) Ingredients: Curing accelerator (E-1) 2PZ-CN (Trade name, manufactured by Shikoku Chemicals Co., Ltd., 1-cyanoethyl-2-phenylimidazole)

[0136] (Preparation of film-like adhesives) The adhesive varnishes of Examples 1-3 and Comparative Example 1 were degassed by letting them stand overnight. A polyethylene terephthalate (PET) film with a release treatment and a thickness of 38 μm was prepared as a support film, and the adhesive varnish after vacuum degassing was applied onto the PET film. The applied adhesive varnish was heated and dried at 90°C for 2 minutes, followed by 130°C for 2 minutes to obtain the film-like adhesives of Examples 1-3 and Comparative Example 1 with a thickness of 5 μm (0.005 mm) in the B stage state. In the film-like adhesives of Examples 1-3 and Comparative Example 1, the thickness of the film-like adhesive was adjusted by the amount of adhesive varnish applied.

[0137] [Calculation of the fracture coefficient m of the film-like adhesive] Samples (width: 5 mm, length: 30 mm, thickness: 0.005 mm) were cut from the film-like adhesives of Examples 1 to 3 and Comparative Example 1. Meanwhile, a frame plate similar in shape to the frame plate 24 shown in Figure 5 was prepared, with a slit (width 3 mm x length 36 mm) formed in the center. The material of the frame plate was polytetrafluoroethylene (PTFE) resin. The sample was attached to the surface of the frame plate with double-sided adhesive tape (see Figure 5). The measurement target area of ​​the sample was the region with a width of 5 mm and a length of 3 mm, which is the slit width.

[0138] A plate with the same configuration as the indentation plate 25 shown in Figure 6 (thickness: 1 mm, width: 15 mm, length: 70 mm) was prepared. The plate angle θ was set to 45°, and the radius of curvature at the tip was set to 10 μm. This plate was mounted on the testing machine. As shown in Figure 5, with the pointed end of the plate facing downwards, the plate was moved from above to below toward the sample, and the load from when the end contacted the sample until the sample fractured was measured using an autograph (A&D Co., Ltd., AZT-CA01, load cell: 50 N). The measurement conditions were as follows: (Conditions for fracture test) Speed ​​mode: constant control Test speed: 10 mm / min Test temperature: -2°C

[0139] TACT (manufactured by A&D Co., Ltd.) was used as the analysis software to obtain measurements of cleavage work W (unit: N・mm), cleavage strength P (unit: N), and plate indentation distance d (unit: mm). The results are shown in Table 2. The values ​​listed in Table 2 are the average values ​​obtained from 3 to 5 measurements using multiple samples prepared under the same conditions. From these values, the cleavage coefficient m (dimensionless) was calculated using equation (X). The results are shown in Table 2. m = [W / (P × L)] × 1000 (X) In equation (X), L represents the length of the sample S when it is cleaved, and is the value calculated in the following equation (Xa) with a slit width S = 3 mm. L = [(S / 2)] ２ +d ２ ] １／２ ×2 (Xa)

[0140]

[0141] As shown in Table 2, the film-like adhesives of Examples 1 to 3 had a smaller cleavage coefficient m compared to the film-like adhesive of Comparative Example 1. This indicates that the film-like adhesives of the examples have excellent cooling cleavage properties and can be applied to semiconductor device manufacturing processes in which cooling expansion is performed. These results confirm that the semiconductor device manufacturing method of this disclosure has excellent cooling cleavage properties.

[0142] 1...Film-like adhesive, 1A...Adhesive layer, 2...Base layer, 3...Adhesive layer, 4...Dicing film, 10...Dicing / die bonding integrated film, 11, 11a, 11b, 11c, 11d, 11e, 11f, 11g, 11h...Semiconductor chip, 12...Support member, 13...Bonding wire, 14...Sealing material, 15, 15a, 15b, 15c, 15d, 15e, 15f, 15g, 15h...Adhesive member, 16...Terminal, 24...Frame plate, 24a...Slit, 25...Insertion plate, 26...End, 27...Protrusion, 28...Double-sided adhesive tape, 30...Component, 100, 110, 120...Semiconductor device, S...Sample, SR...Measurement target part.

Claims

1. A step of preparing a laminate comprising a dicing-die bonding integrated film having a base layer, an adhesive layer, and an adhesive layer in that order, and a plurality of semiconductor chips formed by framing a semiconductor wafer, provided on the adhesive layer of the dicing-die bonding integrated film; a step of expanding the adhesive layer of the laminate under cooling conditions to frame it and produce a plurality of semiconductor chips with adhesive pieces; a step of picking up a first semiconductor chip and a first semiconductor chip with adhesive pieces having a first adhesive piece from the plurality of semiconductor chips with adhesive pieces from the adhesive layer; and a step of bonding the first semiconductor chip with adhesive pieces to a support member via the first adhesive piece, wherein the adhesive layer contains a thermosetting resin component and an elastomer, and may further contain an inorganic filler, the amount of the inorganic filler is 0 to 5% by mass based on the total amount of the adhesive layer, and the elastomer contains a (meth)acrylate polymer containing structural units derived from (meth)acrylate having epoxy groups. A method for manufacturing a semiconductor device, wherein the content of structural units derived from the epoxy group-containing (meth)acrylate is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer.

2. A laminate comprising: a step of preparing a dicing-die bonding integrated film having a base layer, an adhesive layer, and an adhesive layer in this order; a step of preparing a laminate comprising a plurality of semiconductor chips formed by fragmenting a semiconductor wafer and provided on the adhesive layer of the dicing-die bonding integrated film; a step of expanding the adhesive layer of the laminate under cooling conditions to fragment a plurality of semiconductor chips with adhesive pieces; a step of picking up a first semiconductor chip and a first semiconductor chip with adhesive pieces having a first semiconductor chip and a first adhesive piece from the plurality of semiconductor chips with adhesive pieces from the adhesive layer; and a step of bonding the first semiconductor chip with adhesive pieces to a support member via the first adhesive piece, wherein the adhesive layer contains a thermosetting resin component and an elastomer, and may further contain an inorganic filler, the amount of the inorganic filler is 0 to 5% by mass based on the total amount of the adhesive layer, and the elastomer contains a (meth)acrylate polymer containing structural units derived from (meth)acrylate having epoxy groups. A method for manufacturing a semiconductor device, wherein the epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more.

3. A laminate comprising: a step of preparing a dicing-die bonding integrated film having a base layer, an adhesive layer, and an adhesive layer in this order; a step of preparing a laminate comprising a plurality of semiconductor chips formed by fragmenting a semiconductor wafer and provided on the adhesive layer of the dicing-die bonding integrated film; a step of expanding the adhesive layer of the laminate under cooling conditions to fragment a plurality of semiconductor chips with adhesive pieces; a step of picking up a first semiconductor chip and a first semiconductor chip with adhesive pieces having a first semiconductor chip and a first adhesive piece from the plurality of semiconductor chips with adhesive pieces from the adhesive layer; and a step of bonding the first semiconductor chip with adhesive pieces to a support member via the first adhesive piece, wherein the adhesive layer contains a thermosetting resin component and an elastomer, and may further contain an inorganic filler, the amount of the inorganic filler is 0 to 5% by mass based on the total amount of the adhesive layer, and the elastomer contains a (meth)acrylate polymer containing structural units derived from (meth)acrylate having epoxy groups. A method for manufacturing a semiconductor device, wherein, in the infrared absorption spectrum of the (meth)acrylate polymer, P(A) is the area of ​​the absorption peak originating from the antisymmetric stretching of the epoxy group, and P(B) is the area of ​​the absorption peak originating from the stretching vibration of the carbonyl group, and P(A) and P(B) satisfy the condition of the following formula (1): P(A) / P(B) ≥ 0.0055 (1) 4. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the thickness of the adhesive layer is 15 μm or less.

5. A method for manufacturing a semiconductor device according to any one of claims 1 to 3, further comprising: a step of thermally curing the first adhesive piece in the first adhesive piece-attached semiconductor chip at a temperature of 100 to 180°C for 15 to 60 minutes; and a step of electrically connecting the first semiconductor chip and the support member with a bonding wire.

6. A method for manufacturing a semiconductor device according to any one of claims 1 to 3, further comprising the step of bonding a second semiconductor chip having a second semiconductor chip and a second adhesive piece, from among the plurality of semiconductor chips with adhesive pieces, to the surface of the first semiconductor chip with adhesive piece bonded to the support member, via the second adhesive piece.

7. A method for manufacturing a semiconductor device according to claim 6, further comprising: a step of thermal curing the first adhesive piece in the first adhesive piece-attached semiconductor chip and the second adhesive piece in the second adhesive piece-attached semiconductor chip at a temperature of 100 to 180°C for 15 to 60 minutes; and a step of electrically connecting the first semiconductor chip and the second semiconductor chip and the support member with bonding wires.

Images