Method for manufacturing a workpiece with a film-like adhesive, method for manufacturing a workpiece with a cured adhesive, film-like adhesive, and film-like adhesive composite sheet

Abstract

To provide a method for manufacturing a workpiece with a film-like adhesive, a method for manufacturing a workpiece with a cured adhesive, a film-like adhesive, and a film-like adhesive composite sheet, which enable faster etching than conventional methods when cutting the film-like adhesive by plasma irradiation. [Solution] A method for manufacturing a workpiece with a film-like adhesive, comprising the steps of irradiating a film-like adhesive 13 exposed between multiple workpieces 90 with plasma from the side of the multiple workpieces 90 to dry etch the film-like adhesive 13 and cut the film-like adhesive 13 along the workpieces 90, wherein the film-like adhesive 13 contains a compound (c) having at least two radical-reactive groups.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a workpiece with a film-like adhesive, a method for manufacturing a workpiece with a cured adhesive, a film-like adhesive, and a film-like adhesive composite sheet.

Background Art

[0002] When manufacturing a semiconductor device, for example, a semiconductor chip with a film-like adhesive provided on the back surface (the surface opposite to the circuit surface) of the semiconductor chip is manufactured, and this is adhered and fixed to a circuit board by the film-like adhesive therein for mounting. The film-like adhesive usually has thermosetting properties and is cured by heating. After adhering the semiconductor chip with the film-like adhesive to the circuit board, the film-like adhesive is thermally cured to fix the semiconductor chip to the circuit board.

[0003] The semiconductor chip with the film-like adhesive can be manufactured, for example, by the following method. That is, first, a film-like adhesive composite sheet (for example, a die bonding sheet) including a support sheet and a film-like adhesive provided on one surface of the support sheet is used. The film-like adhesive therein is attached to the back surface (the surface opposite to the circuit surface) of the semiconductor wafer. Next, on the support sheet, the semiconductor wafer is divided to produce semiconductor chips, and the film-like adhesive is cut to produce a plurality of the semiconductor chips with the film-like adhesive on the support sheet (see Patent Document 1, etc.).

[0004] Also, the semiconductor chip with the film-like adhesive can be manufactured by the following method. That is, first, a large number of parallel grooves are formed in two directions perpendicular to each other from the circuit surface to the back surface of the semiconductor wafer. At this time, the interval between adjacent grooves is adjusted so that semiconductor chips of the desired size can be obtained. Next, after forming the grooves, a backgrind tape is attached to the circuit surface of the semiconductor wafer, and then the back surface of the semiconductor wafer is ground. The back surface is ground until the grooves appear, or, before the grooves appear, the semiconductor wafer is divided at the groove formation sites by vibrations applied to the semiconductor wafer while the back surface is being ground, thereby producing a large number of aligned semiconductor chips. These semiconductor chips are held together by the backgrind tape.

[0005] Next, a film-like adhesive composite sheet (for example, a die bonding sheet) is used, which comprises a support sheet and a film-like adhesive provided on one surface of the support sheet. The film-like adhesive within the composite sheet is then attached to the back surface (in other words, the grinding surface) of the aforementioned number of semiconductor chips. Next, the backgrind tape is removed from these semiconductor chips. At this stage, these semiconductor chips are held in place by a film-like adhesive. Next, a laser beam is irradiated onto the portion of the film-like adhesive that is exposed between multiple semiconductor chips, cutting the film-like adhesive along the semiconductor chips. As a result, a number of semiconductor chips with film-like adhesive attached, each comprising a semiconductor chip and the cut film-like adhesive provided on the back surface of the semiconductor chip, are obtained on a support sheet.

[0006] These film-like adhesive semiconductor chips are pulled away from the support sheet and picked up to obtain the desired film-like adhesive semiconductor chip. To facilitate this pick-up, the film-like adhesive may also have energy-ray curing properties in addition to the thermosetting properties described above, allowing it to harden when irradiated with energy rays such as ultraviolet light. By energy-ray curing the film-like adhesive before pick-up, the peeling force between the energy-ray cured film-like adhesive (adhesive-cured product) and the support sheet is reduced within an appropriate range, regardless of the type of support sheet, so that the semiconductor chip equipped with the cured product (adhesive-cured semiconductor chip) can be easily picked up from the support sheet (see Patent Document 2, etc.). Such energy-ray cured film-like adhesives (adhesive-cured products) can still be used as film-like adhesives.

[0007] The above-mentioned splitting of semiconductor wafers and cutting of film-like adhesives can be carried out by various methods. For example, blade dicing, which uses a blade, is a widely known method for continuously splitting semiconductor wafers and cutting film-like adhesives, but plasma dicing, which uses plasma irradiation, is also known. In the case of plasma dicing, for example, plasma generated from SF6 gas is commonly used for splitting semiconductor wafers, and plasma generated from O2 gas has been attempted for cutting film-like adhesives (see Patent Documents 3 and 4, Non-Patent Document 1, etc.). [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2013-194103 [Patent Document 2] Japanese Patent Publication No. 2005-322853 [Patent Document 3] Japanese Patent Publication No. 2004-172364 [Patent Document 4] Japanese Patent Publication No. 2016-171262 [Non-patent literature]

[0009] [Non-Patent Document 1] Frank Wei,et. al., PlasmaDicingFullyIntegratedProcess-FlowsSuitablefor BEOL Advanced Packaging Fabrications, 2017 IEEE 67th Electronic Components and Technology Conference (ECTC), DOI:10.1109 / ECTC.2017.269 [Overview of the project] [Problems that the invention aims to solve]

[0010] Figure 5 is a schematic cross-sectional view illustrating a typical example of a conventional plasma dicing method in which plasma P is irradiated onto a semiconductor wafer through a mask 7 to divide the semiconductor wafer and form a semiconductor chip 90, and then plasma P is irradiated onto a film-like adhesive 13 through the semiconductor chip 90 to attempt to cut the film-like adhesive 13.

[0011] By irradiating the semiconductor wafer exposed between multiple masks 7 via the mask 7 with plasma P, the semiconductor wafer can be dry-etched along the shape of the gap between the multiple masks 7, and a semiconductor chip 90 of the same shape can be formed along the shape of the multiple masks 7.

[0012] However, even when plasma P is irradiated onto the film-like adhesive 13 via the semiconductor chip 90, there is a problem in that the etching rate in the thickness direction of the film-like adhesive 13 is slow.

[0013] Up to this point, we have explained the problems encountered when manufacturing semiconductor devices, using the example of manufacturing semiconductor chips with film-like adhesive or semiconductor chips with cured adhesive from semiconductor wafers. However, similar problems can occur when manufacturing various substrate devices, not limited to semiconductor devices. In other words, the above problems can also occur when manufacturing workpieces with film-like adhesive or workpieces with cured adhesive, which consist of a workpiece obtained by processing a workpiece and a film-like adhesive applied to the workpiece.

[0014] The present invention aims to provide a method for manufacturing a workpiece with a film-like adhesive, a method for manufacturing a workpiece with a cured adhesive, a film-like adhesive used in these, and a film-like adhesive composite sheet, which enable a faster etching rate than conventional methods when cutting the film-like adhesive by plasma irradiation using a workpiece group holder comprising a support sheet, a film-like adhesive provided on one surface of the support sheet, and a plurality of workpieces held in alignment on the side of the film-like adhesive opposite to the side of the support sheet. [Means for solving the problem]

[0015] To solve the above problems, the present invention employs the following configuration. [1] A workpiece group holder comprising a support sheet, a film-like adhesive provided on one surface of the support sheet, and a plurality of workpieces held in alignment on the side of the film-like adhesive opposite to the side of the support sheet, is used to produce a workpiece group holder with film-like adhesive in which a plurality of workpieces with film-like adhesive provided on one surface of the support sheet are held in alignment, by irradiating the film-like adhesive exposed between the plurality of workpieces in the workpiece group holder with plasma from the side of the plurality of workpieces, dry etching the film-like adhesive and cutting the film-like adhesive along the workpieces, The method for manufacturing a workpiece with a film-shaped adhesive contains a compound (c) having at least two radical-reactive groups. [2] The method for manufacturing a workpiece with a film-shaped adhesive according to [1], wherein the film-shaped adhesive further contains a photopolymerization initiator (d) having a boiling point of 300 °C or higher. [3] The method for manufacturing a workpiece with a film-shaped adhesive according to [1] or [2], wherein the film-shaped adhesive further contains an acrylic resin (a1) having a structural unit derived from an (alkyl (meth)acrylate). [4] The method for manufacturing a workpiece with a film-shaped adhesive according to [3], wherein the alkyl group constituting the alkyl ester in the (alkyl (meth)acrylate) has 11 or fewer carbon atoms. [5] The method for manufacturing a workpiece with a film-shaped adhesive according to [3] or [4], wherein the weight-average molecular weight of the acrylic resin (a1) is 300,000 or more. [6] Using a workpiece group holder with a film-shaped adhesive obtained by the manufacturing method according to any one of [1] to [5], irradiating energy rays from the side of the support sheet of the workpiece group holder with the film-shaped adhesive to cure the film-shaped adhesive, and producing a workpiece group holder with cured adhesives in which a plurality of workpieces with cured adhesives provided on one surface of the support sheet are aligned and held. The method for manufacturing a workpiece with a cured adhesive includes The compound (c) has energy-ray curability. The method for manufacturing a workpiece with a cured adhesive. [7] A film-shaped adhesive containing a compound (c) having at least two radical-reactive groups and used in the manufacturing method according to any one of [1] to [5]. [8] A film-shaped adhesive composite sheet including a support sheet and a film-shaped adhesive provided on one surface of the support sheet, wherein the film-shaped adhesive contains a compound (c) having at least two radical-reactive groups and is used in the manufacturing method according to any one of [1] to [5]. [Advantages of the Invention]

[0016] The present invention provides a method for manufacturing a workpiece with a film-like adhesive, a method for manufacturing a workpiece with a cured adhesive, and a film-like adhesive and a film-like adhesive composite sheet used therein, which enable a faster etching rate than conventional methods when cutting the film-like adhesive by plasma irradiation using a workpiece group holder comprising a support sheet, a film-like adhesive provided on one surface of the support sheet, and a plurality of workpieces held in alignment on the side of the film-like adhesive opposite to the side of the support sheet. [Brief explanation of the drawing]

[0017] [Figure 1A] This is a schematic cross-sectional view illustrating a part of the process in an example of a method for manufacturing a workpiece with a film-like adhesive according to one embodiment of the present invention. [Figure 1B] This is a schematic cross-sectional view illustrating a part of the process in an example of a method for manufacturing a workpiece with a film-like adhesive according to one embodiment of the present invention. [Figure 1C] This is a schematic cross-sectional view illustrating a part of the process in an example of a method for manufacturing a workpiece with an adhesive curing product according to one embodiment of the present invention. [Figure 1D] This is a schematic cross-sectional view illustrating a part of the process in an example of a method for manufacturing a workpiece with an adhesive curing product according to one embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view showing an example of a film-like adhesive according to one embodiment of the present invention. [Figure 3] This is a schematic cross-sectional view showing an example of a film-like adhesive composite sheet using a film-like adhesive according to one embodiment of the present invention. [Figure 4] This is a schematic cross-sectional view illustrating a method for measuring the etching rate when a plasma is irradiated onto a film-like adhesive according to one embodiment of the present invention. [Figure 5]This is a schematic cross-sectional view illustrating a typical example of a conventional plasma dicing method in which plasma P is irradiated onto a film-like adhesive 13 via a semiconductor chip 90 to attempt to cut the film-like adhesive 13. [Modes for carrying out the invention]

[0018] ◇Method for manufacturing workpieces with film-like adhesive A method for manufacturing a workpiece with a film-like adhesive according to one embodiment of the present invention includes a workpiece group holder comprising a support sheet, a film-like adhesive provided on one surface of the support sheet, and a plurality of workpieces held in alignment on the side of the film-like adhesive opposite to the side of the support sheet, wherein the workpiece group holder is manufactured by irradiating the film-like adhesive exposed between the plurality of workpieces in the workpiece group holder with plasma from the side of the plurality of workpieces, dry etching the film-like adhesive and cutting the film-like adhesive along the workpieces, thereby manufacturing a workpiece group holder with a film-like adhesive in which a plurality of workpieces with film-like adhesive provided on one surface of the support sheet are held in alignment, and the film-like adhesive contains a compound (c) having at least two radical-reactive groups.

[0019] Since the film-like adhesive contains a compound (c) having at least two radical-reactive groups, when plasma is irradiated from the side of the workpieces onto the film-like adhesive exposed between the workpieces, radicals are generated on the exposed portion of the film-like adhesive between the workpieces. As a result, the film-like adhesive hardens, making it possible to create a cured material that is more brittle than the film-like adhesive, and thus increasing the etching rate.

[0020] In this specification, a workpiece is defined as a product obtained by machining a workpiece. Examples of the aforementioned workpieces include wafers and semiconductor device panels.

[0021] Examples of the aforementioned wafers include semiconductor wafers composed of elemental semiconductors such as silicon, germanium, and selenium, and compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; and insulating wafers composed of insulators such as sapphire and glass. For example, if the workpiece is a semiconductor wafer, the workpiece could be a semiconductor chip. A circuit is formed on one side of these wafers, and in this specification, the side of the wafer on which the circuit is formed is referred to as the "circuit side." The side of the wafer opposite to the circuit side is referred to as the "back side." A wafer is divided into chips by means of dicing or other methods. In this specification, as with the wafer, the side of the chip on which the circuit is formed is referred to as the "circuit side," and the side of the chip opposite the circuit side is referred to as the "back side." Both the circuit surface of the wafer and the circuit surface of the chip are provided with protruding electrodes such as bumps and pillars. Preferably, these protruding electrodes are made of solder.

[0022] The aforementioned semiconductor device panel is handled during the manufacturing process of a semiconductor device. A specific example of such a panel is a semiconductor device in which one or more electronic components are sealed with a sealing resin, and multiple such semiconductor devices are arranged planarly within a circular, rectangular, or other shaped area.

[0023] In this specification, "substrate device" means a device constructed by bonding and fixing a workpiece with a film-like adhesive or a workpiece with a cured adhesive to a circuit board using the film-like adhesive or the cured adhesive. For example, if a semiconductor wafer is used as the workpiece, a semiconductor device can be considered as the substrate device.

[0024] The film-like adhesive can be laminated with a support sheet to form a film-like adhesive composite sheet, which will be described later. This film-like adhesive composite sheet can be used in the same way as known die bonding sheets.

[0025] <Manufacturing method for semiconductor chips with film-like adhesive (Manufacturing method (1))> A method for manufacturing a semiconductor chip with a film-like adhesive, where the workpiece is a semiconductor wafer and the workpiece is a semiconductor chip, includes a semiconductor chip group holder comprising a support sheet, a film-like adhesive provided on one surface of the support sheet, and a plurality of semiconductor chips held in alignment on the side of the film-like adhesive opposite to the side of the support sheet, wherein the semiconductor chip group holder is manufactured by irradiating the film-like adhesive exposed between the plurality of semiconductor chips in the semiconductor chip group holder with plasma from the side of the plurality of semiconductor chips, dry etching the film-like adhesive, and cutting the film-like adhesive along the semiconductor chips, thereby manufacturing a semiconductor chip group holder with a film-like adhesive in which the plurality of semiconductor chips with film-like adhesive provided on one surface of the support sheet are held in alignment, wherein the film-like adhesive contains a compound (c) having at least two radical-reactive groups.

[0026] The manufacturing method (1) will be explained below with reference to the drawings. Figures 1A to 1C are cross-sectional views illustrating an example of manufacturing method (1). Here, we will explain manufacturing method (1) using the film-like adhesive composite sheet 101 shown in Figure 3. Please note that the diagrams used in the following explanation may be enlarged for convenience in order to make the features of the present invention easier to understand, and the dimensional ratios of each component may not be the same as in reality.

[0027] First, prepare a semiconductor chip group holder 901 as shown in Figure 1A. The semiconductor chip group holder 901 is constructed by holding a plurality of semiconductor chips 90 in an aligned state on the first surface 13a of the film-like adhesive 13 in the film-like adhesive composite sheet 101. All of the semiconductor chips 90 are held on the first surface 13a of the film-like adhesive 13 on their back surfaces 90b.

[0028] The semiconductor chip group holder 901 can be fabricated by known methods. For example, before dividing a semiconductor wafer into semiconductor chips 90, numerous parallel grooves are formed in two directions perpendicular to each other, from the circuit side toward the back side (a process known as half-cutting). At this time, the spacing between adjacent grooves is adjusted so that a semiconductor chip 90 of the desired size is obtained. The circuit side and back side of the semiconductor wafer become the circuit side 90a and back side 90b of the semiconductor chip 90, respectively, after the semiconductor wafer is divided. Next, after forming the grooves, a backgrind tape is applied to the circuit surface of the semiconductor wafer, and then the back surface of the semiconductor wafer is ground. The back surface is ground until the grooves appear, or, before the grooves appear, the semiconductor wafer is divided at the groove formation site by vibrations applied to the semiconductor wafer while the back surface is being ground. Based on the above, multiple aligned semiconductor chips 90, held in place by backgrind tape, are fabricated.

[0029] Next, using one film-like adhesive composite sheet 101, the first surface 13a of the film-like adhesive 13 within it is collectively attached to the back surface 90b (in other words, the grinding surface) of the multiple semiconductor chips 90 mentioned above. Next, the backgrind tape is removed from these semiconductor chips 90. Based on the above, the semiconductor chip group holder 901 shown in Figure 1A is obtained.

[0030] The semiconductor chip group holder 901 shown in Figure 1A can also be obtained, in addition to the method described above, by, for example, using a single film-like adhesive composite sheet 101, attaching the first surface 13a of the film-like adhesive 13 within it to the back surface of a semiconductor wafer, and then irradiating the semiconductor wafer with plasma from the circuit side to dry etch it, thereby dividing the semiconductor wafer. In this case, the step of dividing the semiconductor wafer by irradiating it with plasma from the circuit side can be performed simultaneously with, or in the same operation as, the step of dry etching the film-like adhesive 13 by irradiating it with plasma from the side of the multiple semiconductor chips 90, as shown below.

[0031] Next, as shown in Figures 1A and 1B, plasma is irradiated from the side of the semiconductor chips 90 to the film-like adhesive 13 exposed between the multiple semiconductor chips 90 in the semiconductor chip group holder 901, thereby dry etching the film-like adhesive 13 and cutting the film-like adhesive 13 along the semiconductor chips 90. As a result, as shown in Figure 1B, multiple semiconductor chips 91 with film-like adhesive are fabricated, each comprising a semiconductor chip 90 and a pre-cut film-like adhesive 133 provided on the back surface 90b of the semiconductor chip 90.

[0032] Since the film-like adhesive 13 contains compound (c) having at least two radical-reactive groups, when plasma is irradiated from the side of the multiple semiconductor chips 90 onto the film-like adhesive 13 exposed between the multiple semiconductor chips 90, radicals are generated on the exposed portion of the film-like adhesive 13 between the multiple semiconductor chips 90. As a result, the film-like adhesive 13 hardens, making it possible to create a cured material that is more brittle than the film-like adhesive 13, and thus increasing the etching rate.

[0033] These multiple semiconductor chips 91 with film-like adhesive are aligned and held on a support sheet 10 (in other words, a substrate 11), and together with the support sheet 10, they constitute a semiconductor chip group holder 903 with film-like adhesive. The first surface 133a and the second surface 133b of the cut film-like adhesive 133 are derived from the first surface 13a and the second surface 13b of the film-like adhesive 13 before cutting, respectively.

[0034] When dry etching the film-like adhesive 13 by irradiating it with plasma from the side of multiple semiconductor chips 90, the plasma irradiation conditions are not particularly limited as long as the film-like adhesive 13 can be sufficiently dry-etched, and can be appropriately selected depending on the type of film-like adhesive 13. For example, when using SF6 gas, the plasma can be irradiated under the conditions of SF6 gas flow rate (sccm) / argon gas flow rate (sccm) being 50 / 3, under a reduced pressure environment of 20 Pa, and with an RF (Radio Frequency) power of 250 W. Similarly, when using O2 gas, the plasma can be irradiated under the conditions of O2 gas flow rate (sccm) / argon gas flow rate (sccm) being 50 / 3, under a reduced pressure environment of 20 Pa, and with an RF (Radio Frequency) power of 250 W.

[0035] In this specification, not only in the case of manufacturing method (1), "pre-cut film-like adhesive" may be simply referred to as "film-like adhesive."

[0036] The semiconductor chip group holder 903 with film adhesive is constructed by holding a plurality of semiconductor chips 91 with film adhesive in an aligned state on the first surface 10a of the support sheet 10. All of the semiconductor chips 91 with film adhesive are held on the first surface 10a of the support sheet 10 by the second surface 133b of the cut film adhesive 133.

[0037] In the semiconductor chip group holder 903 with film adhesive shown in Figure 1B, the semiconductor chips 91 with film adhesive can be pulled away from the support sheet 10 and picked up. At this time, delamination occurs between the second surface 133b of the cut film adhesive 133 in the semiconductor chip 91 and the first surface 10a of the support sheet 10 (the first surface 11a of the base material 11). If necessary, the support sheet 10 can be expanded to increase the distance between the semiconductor chips 91 with film adhesive before picking them up.

[0038] <Etching rate when plasma is irradiated onto a film-like adhesive> Here, we will explain the method for measuring the etching rate when plasma is irradiated onto a film-like adhesive, referring to Figure 4.

[0039] First, as shown in Figure 4(a), a test specimen 6 is prepared, comprising a film-like adhesive 13, a mask 7 attached to one side (sometimes referred to as the "first side" in this specification) 13a of the film-like adhesive 13, and a support 8 attached to the other side of the film-like adhesive 13.

[0040] The material of the mask 7 is not particularly limited as long as it can suppress the transmission of plasma, and may be, for example, an adhesive tape containing a high-strength resin such as polyimide as its main component. The shape and size of the mask 7 are not particularly limited, as long as the exposed area of ​​the first surface 13a of the film-like adhesive 13 and the area masked (shielded) by the mask 7 are both of sufficient size.

[0041] The support 8 is not particularly limited as long as it can hold the film-like adhesive 13 when irradiated with plasma, and may be, for example, a sheet or plate made of resin or an inorganic material. The support 8 may be, for example, a semiconductor wafer or a semiconductor chip.

[0042] Then, the test piece 6 is irradiated with plasma P from the first surface 13a of the film-like adhesive 13. This etches the areas of the film-like adhesive that are not masked by the mask 7, as shown in Figure 4(b). After irradiation with plasma P (after etching), as shown in Figure 4(c), the mask 7 is removed from the film-like adhesive 13, and the height difference between the initial first surface 13a of the film-like adhesive 13 (the surface of the film-like adhesive 13 that was masked by the mask 7) and the etched surface 13a' of the film-like adhesive 13 (the surface of the film-like adhesive 13 that was not masked by the mask 7), i.e., the etching distance L, is measured. The etching distance L can be measured as surface roughness, for example, using a surface roughness measuring instrument. Then, the etching rate is calculated from the plasma irradiation time (etching time) t and L by L / t, and this is adopted as the etching rate of the film-like adhesive.

[0043] To improve the accuracy of etching rate measurement, it is preferable that the etching distance L be 3 μm or greater.

[0044] For example, with respect to the film-like adhesive, the etching rate measured using plasma generated from O2 gas under the conditions described in the examples below can preferably be 1.0 μm / min or higher, more preferably 1.8 μm / min or higher, and even more preferably 2.3 μm / min or higher. On the other hand, a film-like adhesive with an etching rate of 3.6 μm / min or lower can be realized more easily.

[0045] When a film-like adhesive exposed between multiple workpieces is irradiated with plasma and the film-like adhesive is dry-etched to cut along the workpiece, the etching rate can be reduced regardless of the type of gas used to generate the plasma by: reducing the number of carbon atoms in the alkyl group constituting the alkyl ester in the constituent unit derived from the alkyl (meth)acrylate in the acrylic resin (a1) to 11 or less; making the alkyl group constituting the alkyl ester branched; assuming a homopolymer as the constituent unit in the acrylic resin (a1) and selecting one whose glass transition temperature is 0°C or higher; increasing the content of the acrylic resin (a1) in the film-like adhesive; and reducing the content of the filler (d) described later in the film-like adhesive. The components of the film-type adhesive will be explained in detail later.

[0046] ◇Method for manufacturing workpieces with cured adhesive A method for manufacturing a workpiece with an adhesive curing product according to one embodiment of the present invention includes the step of using a workpiece group holder with a film-like adhesive, obtained by the method for manufacturing a workpiece with a film-like adhesive according to the above embodiment, in which a plurality of workpieces with film-like adhesive are arranged and held on one surface of the support sheet, to irradiate the workpiece group holder with a film-like adhesive from the side of the support sheet to cure the film-like adhesive, thereby producing a workpiece group holder with an adhesive curing product in which a plurality of workpieces with adhesive curing products are arranged and held on one surface of the support sheet, wherein compound (c) is energy-ray curable. By curing the film-like adhesive with an energy ray, the adhesive force between the adhesive curing product and the support sheet can be reduced, so that the semiconductor chip with the adhesive curing product can be easily pulled away from the support sheet and picked up.

[0047] In this specification, "film adhesive" means a film adhesive that has not undergone both intentional energy ray curing and intentional thermal curing, unless otherwise specified. Unless otherwise specified, "cured adhesive product" refers to an energy-ray cured product of a film-type adhesive. In this specification, "energy beam" means an electromagnetic wave or charged particle beam that has an energy quantum. Examples of energy beams include ultraviolet rays, radiation, and electron beams. Ultraviolet rays can be irradiated, for example, by using high-pressure mercury lamps, fusion lamps, xenon lamps, black lights, or LED lamps as ultraviolet light sources. Electron beams can be irradiated using those generated by electron accelerators, etc. In this specification, "energy ray curable" means the property of hardening when irradiated with energy rays, and "non-energy ray curable" means the property of not hardening even when irradiated with energy rays. In this specification, "thermosetting" means the property of hardening upon heating.

[0048] <Manufacturing method for semiconductor chips with adhesive curing material (Manufacturing method (2))> A method for manufacturing a semiconductor chip with adhesive curing when the workpiece is a semiconductor chip and the workpiece with film adhesive is a semiconductor chip with film adhesive, includes the step of using a semiconductor chip group holder with film adhesive obtained by the above-described manufacturing method (1), in which a plurality of semiconductor chips with film adhesive are aligned and held on one surface of the support sheet, to irradiate the semiconductor chip group holder with film adhesive from the side of the support sheet with energy rays to cure the film adhesive, thereby producing a semiconductor chip group holder with adhesive curing in which a plurality of semiconductor chips with adhesive curing are aligned and held on one surface of the support sheet, wherein compound (c) is energy ray curable. By curing the film adhesive with energy rays, the adhesive force between the adhesive curing and the support sheet can be reduced, so that the semiconductor chip with adhesive curing can be easily pulled away from the support sheet and picked up.

[0049] The manufacturing method (2) will be explained below with reference to the drawings. Figures 1B to 1D are cross-sectional views illustrating an example of manufacturing method (2). Here, we will describe manufacturing method (2) using the semiconductor chip group holder 903 with film adhesive shown in Figure 1B.

[0050] Using the semiconductor chip group holder 903 obtained by the above-described manufacturing method (1), in which a plurality of semiconductor chips 91 with film-like adhesive attached, which are provided on the first surface 10a of the support sheet 10, are held in an aligned state, the cut film-like adhesive 133 is cured by irradiating the semiconductor chip group holder 903 with energy rays from the side of the support sheet 10 to obtain a cut cured adhesive product 134. As a result, as shown in Figure 1C, multiple semiconductor chips 92 with adhesive curing material are fabricated, each comprising a semiconductor chip 90 and a cut adhesive curing material 134 provided on the back surface 90b of the semiconductor chip 90. These multiple semiconductor chips 92 with adhesive curing material are aligned and held on a support sheet 10 (in other words, a substrate 11), and together with the support sheet 10, constitute an adhesive curing material semiconductor chip group holder 904. The first surface 134a and the second surface 134b of the cut and cured adhesive product 134 originate from the first surface 133a and the second surface 133b of the cut and cured film-like adhesive 133, respectively.

[0051] Next, as shown in Figure 1D, the semiconductor chip 92 with the cured adhesive is pulled away from the support sheet 10 and picked up. At this time, delamination occurs between the second surface 134b of the cured adhesive 134 in the semiconductor chip 92 and the first surface 10a of the support sheet 10. This makes it possible to remove the desired semiconductor chip 92 with the cured adhesive.

[0052] By curing the pre-cut film-like adhesive 133 to form a pre-cut cured adhesive product 134, the adhesive force between the pre-cut cured adhesive product 134 and the support sheet 10 can be reduced, making it easy to separate and pick up the semiconductor chip 92 with the cured adhesive product attached from the support sheet 10.

[0053] The semiconductor chip 92 with the adhesive cured material can be picked up by known methods. For example, the semiconductor chip 92 with the adhesive cured material attached can be picked up by pushing it up from the support sheet 10 side using a pin (not shown) through the support sheet 10, and then using a separation means 9 such as a vacuum collet to separate the semiconductor chip 92 with the adhesive cured material attached in the direction of arrow F.

[0054] ◇Film-type adhesive A film-like adhesive according to one embodiment of the present invention contains a compound (c) having at least two radical-reactive groups, and is used in the method for manufacturing a workpiece with a film-like adhesive or a workpiece with a cured adhesive according to the above embodiment.

[0055] The film-like adhesive of this embodiment contains compound (c) having at least two radical-reactive groups. Because the film-like adhesive of this embodiment contains compound (c) having at least two radical-reactive groups, when plasma is irradiated from the side of the workpieces onto the film-like adhesive exposed between the workpieces, radicals are generated on the exposed portion of the film-like adhesive between the workpieces, and as a result the film-like adhesive hardens, making the hardened material more brittle than the film-like adhesive and increasing the etching rate. It is preferable that compound (c) is further energy-ray curable.

[0056] The film-like adhesive of this embodiment is suitable for cutting along the workpieces by using the workpiece group holder and irradiating the film-like adhesive exposed between the multiple workpieces in the workpiece group holder with plasma from the side of the multiple workpieces to dry etch the exposed portion of the film-like adhesive.

[0057] In this embodiment, the film-like adhesive preferably possesses both energy ray curability and thermosetting properties. During the manufacturing process of a substrate device, a workpiece with the film-like adhesive or a workpiece with the cured adhesive can be mounted on a circuit board by bonding it to the circuit board using the film-like adhesive or cured adhesive. Furthermore, if the cured adhesive (energy ray cured film-like adhesive) or the film-like adhesive is thermosetting, the energy rays and thermosetting material formed by thermosetting the cured adhesive or film-like adhesive after bonding, or the thermosetting material, have high impact resistance and maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

[0058] The aforementioned film-like adhesive preferably has pressure-sensitive adhesive properties. A film-like adhesive that has both thermosetting and pressure-sensitive adhesive properties can be applied to various substrates by lightly pressing it when it has not been cured by heating. The film-like adhesive may also be one that can be applied to various substrates by softening it by heating.

[0059] When the cured product of the aforementioned film-like adhesive is actually used, the curing conditions for curing the film-like adhesive to form the cured product are not particularly limited, as long as the degree of curing of the cured product is sufficiently high, and can be appropriately selected according to the type of film-like adhesive. When energy rays are irradiated onto a film-like adhesive from the side of the support sheet, the irradiance of the energy rays is 60-320 mW / cm². 2 Preferably, the amount of light from the energy ray during the energy ray curing process is 100 to 1000 mJ / cm². 2 It is preferable that this be the case. The heating temperature during the thermal curing of the adhesive cured product and the film-like adhesive is preferably 100 to 200°C. The heating time during the thermal curing is preferably 0.5 to 5 hours.

[0060] In this specification, the characteristic of being able to properly pick up an object, such as a workpiece with a cured adhesive attached, from a support sheet is sometimes referred to as "pickup capability."

[0061] Further details regarding the components of the film-type adhesive will be explained later.

[0062] <Example of film-type adhesive> Figure 2 is a schematic cross-sectional view showing an example of the film-like adhesive of this embodiment. Please note that the diagrams used in the following explanation may be enlarged for convenience in order to make the features of the present invention easier to understand, and the dimensional ratios of each component may not be the same as in reality.

[0063] The film-like adhesive 13 shown in Figure 2 has a first release film 151 on one side (sometimes referred to as the "first side" in this specification) 13a and a second release film 152 on the other side (sometimes referred to as the "second side" in this specification) 13b opposite to the first side 13a. Such a film-like adhesive 13 is suitable for storage, for example, in roll form.

[0064] The first release film 151 and the second release film 152 may both be known types. The first release film 151 and the second release film 152 may be the same as each other, or they may be different from each other, for example, having different peeling forces required to peel them off the film-like adhesive 13. It is preferable that both the first release film 151 and the second release film 152 are release films constructed by forming a silicone-based release agent layer on one side of a polyethylene terephthalate film (by silicone treatment).

[0065] In the film-like adhesive 13 shown in Figure 2, both the first release film 151 and the second release film 152 are removed, and one of the resulting exposed surfaces becomes the surface to be attached to the workpiece or workpiece, while the other surface may be, for example, the surface to be attached to the support sheet described later.

[0066] Figure 2 shows an example where the release film is provided on both sides (first surface 13a, second surface 13b) of the film-like adhesive 13. However, the release film may be provided on only one side of the film-like adhesive 13, that is, only the first surface 13a or only the second surface 13b.

[0067] <Other components of film-type adhesives> The film-like adhesive may consist of one layer (single layer) or of two or more layers. If the film-like adhesive consists of multiple layers, these layers may be identical or different, and there are no particular limitations on the combination of these layers.

[0068] In this specification, not only in the case of film-like adhesives, "multiple layers may be identical or different from one another" means "all layers may be identical, all layers may be different, or only some layers may be identical," and further, "multiple layers are different from one another" means "at least one of the constituent materials and thickness of each layer is different from the other."

[0069] The thickness of the film-like adhesive is preferably 1 to 70 μm, more preferably 2 to 50 μm, and particularly preferably 3 to 30 μm. When the thickness of the film-like adhesive is above the lower limit, the strength of the film-like adhesive is increased, and the effects obtained by using the film-like adhesive are also increased. When the thickness of the film-like adhesive is below the upper limit, it is avoided that the thickness of the film-like adhesive and its cured product becomes excessive. Here, "thickness of the film adhesive" refers to the total thickness of the film adhesive. For example, the thickness of a multi-layered film adhesive refers to the total thickness of all the layers that make up the film adhesive.

[0070] In this specification, unless otherwise specified, "thickness" refers to the average of the thicknesses measured at five randomly selected locations on the object, and can be obtained using a constant-pressure thickness measuring instrument in accordance with JIS K7130.

[0071] <<Adhesive Composition>> The aforementioned film-like adhesive can be formed using an adhesive composition containing its constituent materials. For example, the adhesive composition can be applied to the surface on which the film-like adhesive is to be formed, and dried as necessary, thereby forming the film-like adhesive in the desired location. The ratio of components that do not vaporize at room temperature in an adhesive composition is usually the same as the ratio of those components in a film-type adhesive.

[0072] In a film-type adhesive, the ratio of the total content of one or more of the following components in the film-type adhesive to the total mass of the film-type adhesive shall not exceed 100% by mass. Similarly, in an adhesive composition, the ratio of the total content of one or more of the following components of the adhesive composition to the total mass of the adhesive composition shall not exceed 100% by mass.

[0073] The adhesive composition may be coated by known methods, such as using various coaters including air knife coaters, blade coaters, bar coaters, gravure coaters, roll coaters, roll knife coaters, curtain coaters, die coaters, knife coaters, screen coaters, Meyer bar coaters, and kiss coaters.

[0074] The drying conditions for the adhesive composition are not particularly limited, but if the adhesive composition contains a solvent as described later, it is preferable to heat dry it. For example, adhesive compositions containing a solvent are preferably dried at 70 to 130°C for 10 seconds to 5 minutes. The components of the film-type adhesive and adhesive composition will be described in detail below.

[0075] Examples of the adhesive composition include a composition containing an acrylic resin (a1) and a compound (c) having at least two radical-reactive groups (which may be abbreviated as "composition (III)" in this specification). Examples of energy-ray curable adhesive compositions (energy-ray curable composition (III)) for forming energy-ray curable film-like adhesives include compositions containing an acrylic resin (a1) and a compound (c) having at least two radical-reactive groups, and it is preferable that the adhesive composition further contains a photopolymerization initiator (d). Examples of thermosetting adhesive compositions (thermosetting composition (III)) for forming thermosetting film-like adhesives include compositions containing an acrylic resin (a1) and a thermosetting component (b), and it is preferable that the adhesive composition further contains a curing accelerator (e). Examples of adhesive compositions for forming a film-like adhesive that has both energy ray curability and thermosetting properties (energy ray curability and thermosetting composition (III)) include compositions containing an acrylic resin (a1), a compound having at least two radical-reactive groups (c), and a thermosetting component (b). Preferably, the adhesive composition further contains either or both of a photopolymerization initiator (d) and a curing accelerator (e). The adhesive composition (composition (III)) preferably has at least thermosetting properties.

[0076] <Acrylic resin (a1)> The acrylic resin (a1) has constituent units derived from an alkyl (meth)acrylate. Preferably, the number of carbon atoms in the alkyl group constituting the alkyl ester in the alkyl (meth)acrylate is 11 or less. In this specification, such an alkyl (meth)acrylate with an alkyl group having 11 or less carbon atoms may be referred to as "alkyl (meth)acrylate (a11)". Acrylic resin (a1) imparts film-forming properties and flexibility to film-like adhesives, and also serves as a component that increases the etching rate when cutting film-like adhesives using plasma.

[0077] In this specification, "(meth)acrylic acid" is a concept that encompasses both "acrylic acid" and "methacrylic acid." This also applies to terms similar to (meth)acrylic acid, such as (meth)acryloyl group.

[0078] The alkyl group constituting the alkyl ester may be linear, branched, or cyclic, and may have both a linear structure (either linear or branched, or both) and a cyclic structure. The cyclic alkyl group may be monocyclic or polycyclic.

[0079] The number of carbon atoms in the linear alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The branched alkyl group preferably has 3 to 11 carbon atoms, and may be, for example, 3 to 8 or 3 to 4 carbon atoms. The number of carbon atoms in the cyclic alkyl group is preferably 3 to 11, and may be, for example, 3 to 8 and 3 to 4. The alkyl group having both a chain-like and a cyclic structure preferably has 4 to 11 carbon atoms, and may be, for example, 4 to 8 and 4 to 6 carbon atoms.

[0080] Examples of alkyl groups having both a linear and a cyclic structure include alkyl groups having a structure in which one or more hydrogen atoms in the linear (linear or branched) alkyl group are substituted with the cyclic alkyl group.

[0081] Examples of alkyl (meth)acrylate esters in which the alkyl group is chain-like (linear or branched) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, tert-pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, and undecyl (meth)acrylate.

[0082] Examples of alkyl (meth)acrylate esters in which the alkyl group is cyclic include isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate.

[0083] The number of branches in the branched alkyl hydrocarbon chain (sometimes simply referred to as "number of alkyl group branches" in this specification) may be 1 or more, and more preferably 2 or more. The greater the number of branches, the faster the etching rate tends to be during plasma dicing of the film-like adhesive. On the other hand, in terms of making the (meth)acrylate alkyl ester easier to manufacture or obtain, it is preferable that the number of branches of the alkyl group is 3 or less. For example, the isobutyl group has 1 branching, and the tert-butyl group has 2 branching.

[0084] In terms of increasing the etching rate during plasma dicing of the film-like adhesive, the alkyl group is preferably linear or branched, and more preferably branched.

[0085] The monomers that make up the acrylic resin (a1) may be just one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0086] The acrylic resin (a1) may or may not have constituent units derived from monomers other than the alkyl (meth)acrylate (a11) mentioned above. Examples of monomers other than the (meth)acrylate alkyl ester (a11) mentioned above include (meth)acrylate hydroxyalkyl esters such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (meth)acrylate alkyl esters in which the alkyl group constituting the alkyl ester has 12 or more carbon atoms; (meth)acrylic acid; itaconic acid; vinyl acetate; acrylonitrile, styrene, N-methylolacrylamide, etc.

[0087] The hydroxyalkyl (meth)acrylate ester is preferably one in which the hydroxyalkyl group is linear (linear or branched), preferably one in which the hydroxyalkyl group has 1 to 11 carbon atoms, and more preferably one in which the hydroxyalkyl group is linear and has 1 to 11 carbon atoms. Examples of hydroxyalkyl groups having 1 to 11 carbon atoms include groups that constitute the alkyl ester in the alkyl (meth)acrylate (a11) and have a structure in which one hydrogen atom is substituted with a hydroxyl group, in the alkyl group having 11 or fewer carbon atoms.

[0088] The acrylic resin (a1) preferably has a constituent unit derived from an alkyl (meth)acrylate (a11) and a constituent unit derived from a hydroxyalkyl (meth)acrylate. In such an acrylic resin (a1), the ratio of the total amount of constituent units derived from (meth)acrylate alkyl ester (a11) and constituent units derived from (meth)acrylate hydroxyalkyl ester to the mass of the acrylic resin (a1) (([Amount of constituent units derived from (meth)acrylate alkyl ester (a11) in the acrylic resin (a1) (parts by mass)] + [Amount of constituent units derived from (meth)acrylate hydroxyalkyl ester in the acrylic resin (a1) (parts by mass)]) / [Mass of acrylic resin (a1) (parts by mass)] × 100) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, and even more preferably 80 to 100% by mass. For example, it may be any of 90 to 100% by mass, 95 to 100% by mass, and 97 to 100% by mass. The higher the ratio of the total amount, the faster the etching rate during plasma dicing of the film-like adhesive.

[0089] When the acrylic resin (a1) has constituent units derived from (meth)acrylate alkyl ester (a11) and constituent units derived from (meth)acrylate hydroxyalkyl ester, the mass ratio of [amount of constituent units derived from (meth)acrylate alkyl ester (a11) (parts by mass)] / [amount of constituent units derived from (meth)acrylate hydroxyalkyl ester (parts by mass)] in the acrylic resin (a1) is preferably 1 to 6, for example, it may be any of 1 to 4, 2 to 5, and 3 to 6. When the mass ratio is above the lower limit, the etching rate during plasma dicing of the film-like adhesive becomes faster. When the mass ratio is below the upper limit, the acrylic resin (a1) is dispersed with high uniformity in composition (III) and the film-like adhesive.

[0090] The acrylic resin (a1) is preferably one in which the amount (parts by mass) of the constituent unit derived from (meth)acrylate (a11) is the largest among all of its constituent units.

[0091] When considering a homopolymer of monomers that induce any of the constituent units in the acrylic resin (a1) as a characteristic feature of the acrylic resin (a1), it is preferable that the glass transition temperature of the homopolymer be 0°C or higher. Because the film-like adhesive contains an acrylic resin (a1) having such monomer-derived constituent units, the etching rate of the film-like adhesive during plasma dicing becomes faster.

[0092] In terms of achieving the above-mentioned effects more effectively, the glass transition temperature of the homopolymer may be, for example, 8°C or higher, 20°C or higher, or 32°C or higher. On the other hand, for example, an acrylic resin (a1) in which the glass transition temperature of the homopolymer is 50°C or lower is more easily manufactured or available.

[0093] The monomer defining the homopolymer (a monomer that induces the constituent unit in the acrylic resin (a1)) is preferably the monomer that induces the constituent unit that is present in the largest amount (parts by mass) in the acrylic resin (a1). When the acrylic resin (a1) has constituent units derived from an alkyl (meth)acrylate (a11), it is preferable that the monomer defining the homopolymer is an alkyl (meth)acrylate (a11).

[0094] The glass transition temperature (Tg) of the acrylic resin (a1) is preferably -60 to 70°C, more preferably -55 to 40°C, for example, -30 to 40°C, -5 to 40°C, and 20 to 40°C, or -55 to 15°C, -55 to -10°C, and -55 to -35°C, or -30 to 15°C. When the Tg of the acrylic resin is above the lower limit, the adhesive strength between the film-like adhesive and the adherend is suppressed, making it easier to pick up the film-like adhesive-coated chip and the adhesive-cured chip from the substrate or dicing sheet described later. When the Tg of the acrylic resin is below the upper limit, the adhesive strength between the film-like adhesive and the chip is improved.

[0095] If the acrylic resin (a1) has two or more constituent units, the glass transition temperature (Tg) of the acrylic resin (a1) can be calculated using Fox's formula. The Tg of the homopolymer of the monomers that derive the constituent units can be the value specified in the Polymer Data Handbook, Adhesion Handbook, or Polymer Handbook.

[0096] The weight-average molecular weight (Mw) of the acrylic resin (a1) is preferably 100,000 or more, more preferably 200,000 or more, and may be, for example, 300,000 or more, or 400,000 or more. The larger the weight-average molecular weight of the acrylic resin (a1), the faster the etching rate tends to be during plasma dicing of the film-like adhesive.

[0097] The upper limit of the weight-average molecular weight of the acrylic resin (a1) is not particularly limited. For example, in terms of ensuring high uniformity dispersion of the acrylic resin (a1) in composition (III) and the film-like adhesive, the weight-average molecular weight of the acrylic resin (a1) is preferably 2,000,000 or less, and may be, for example, 1,500,000 or less, 1,300,000 or less, or 1,000,000 or less.

[0098] Furthermore, as the weight-average molecular weight of the acrylic resin (a1) increases within the above numerical range, the shape stability (stable over time during storage) of the film-like adhesive improves, and as it decreases, the film-like adhesive becomes more easily conformable to the uneven surface of the adherend.

[0099] In this specification, not only in the case of acrylic resin (a1), but unless otherwise specified, "weight-average molecular weight" refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0100] In the film-like adhesive, the ratio of the acrylic resin (a1) content to the total mass of the film-like adhesive is preferably 10 to 40% by mass, and may be, for example, 10 to 30% by mass or 20 to 40% by mass. When the ratio is above the lower limit, the film-forming properties and flexibility of the film-like adhesive, as well as the etching rate of the film-like adhesive during plasma dicing, are both improved. When the ratio is below the upper limit, excessive use of acrylic resin (a1) is suppressed.

[0101] In the above-mentioned film-like adhesive, the ratio of the acrylic resin (a1) content to the total mass of the film-like adhesive is equivalent to saying that in composition (III), the ratio of the acrylic resin (a1) content to the total content of all components other than the solvent is preferably 10 to 40% by mass, and may be, for example, 10 to 30% by mass and 20 to 40% by mass. This is based on the fact that, in the process of removing the solvent from a solvent-containing resin composition to form a resin film, the amount of components other than the solvent usually does not change, and the ratio of the contents of non-solvent components is the same in the resin composition and the resin film. Therefore, in this specification, not limited to the case of film-like adhesives, the content of non-solvent components will mainly refer to the content in the resin film obtained by removing the solvent from the resin composition.

[0102] <Thermosetting component (b)> Thermosetting component (b) is a component that has thermosetting properties and is used to heat-cur the film-like adhesive. The thermosetting component (b) contained in composition (III) and the film-like adhesive may be one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0103] Examples of the thermosetting component (b) include epoxy-based thermosetting resins, thermosetting polyimide resins, and unsaturated polyester resins, with epoxy-based thermosetting resins being preferred. In this specification, thermosetting polyimide resin is a general term encompassing a polyimide precursor and a thermosetting polyimide, both of which form a polyimide resin through thermosetting.

[0104] [Epoxy thermosetting resin] The epoxy-based thermosetting resin comprises an epoxy resin (b1) and a thermosetting agent (b2). The epoxy thermosetting resin contained in composition (III) and the film-like adhesive may be one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0105] (Epoxy resin (b1)) Examples of epoxy resins (b1) include well-known ones, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, orthocresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and other bifunctional or more epoxy compounds.

[0106] The number-average molecular weight of the epoxy resin (b1) is not particularly limited, but is preferably 300 to 30000 from the viewpoint of the curability of the film-like adhesive and the strength and heat resistance of the cured product of the film-like adhesive. The epoxy equivalent of epoxy resin (b1) is preferably 100 to 1000 g / eq, and may be, for example, 100 to 600 g / eq and 150 to 300 g / eq.

[0107] The epoxy resin (b1) contained in composition (III) and the film-like adhesive may be one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0108] The composition (III) and the film-like adhesive preferably contain a dicyclopentadiene type epoxy resin and a bisphenol F type epoxy resin as the epoxy resin (b1). The inclusion of such a combination of epoxy resins (b1) in the film-like adhesive improves the pickability of the workpiece with the film-like adhesive or the workpiece with the cured adhesive.

[0109] When composition (III) and the film-like adhesive contain a dicyclopentadiene type epoxy resin and a bisphenol F type epoxy resin, the content of the dicyclopentadiene type epoxy resin in composition (III) and the film-like adhesive is preferably 3 to 12 times the mass of the content of the bisphenol F type epoxy resin, for example, it may be 5 to 12 times the mass and 7 to 12 times the mass, or 3 to 10 times the mass and 3 to 8.5 times the mass, or 5 to 10 times the mass and 7 to 8.5 times the mass.

[0110] When composition (III) and the film-like adhesive contain a dicyclopentadiene type epoxy resin and a bisphenol F type epoxy resin, the ratio of the total content of the dicyclopentadiene type epoxy resin and the bisphenol F type epoxy resin to the content of epoxy resin (b1) in composition (III) and the film-like adhesive is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more. When the ratio is above the lower limit, the effects obtained by the film-like adhesive containing the dicyclopentadiene type epoxy resin and the bisphenol F type epoxy resin are significantly enhanced. On the other hand, the aforementioned ratio is 100% by mass or less.

[0111] (Thermosetting agent (b2)) The thermosetting agent (b2) is a curing agent for epoxy resin (b1). Examples of the thermosetting agent (b2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and groups in which an acid group has been converted to an anhydride. It is preferable that the functional group is a phenolic hydroxyl group, an amino group, or a group in which an acid group has been converted to an anhydride, and more preferably a phenolic hydroxyl group or an amino group.

[0112] Examples of thermosetting agents (b2) that include phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Examples of amine-based curing agents containing an amino group among the thermosetting agents (b2) include dicyandiamide (DICY).

[0113] The hydroxyl group equivalent of the thermosetting agent (b2) is preferably 10 to 120 g / eq, and may be, for example, 10 to 60 g / eq and 10 to 40 g / eq.

[0114] Among the thermosetting agents (b2), the number average molecular weight of the resin components, such as polyfunctional phenolic resins, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins, is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000. The molecular weight of the non-resin component of the thermosetting agent (b2), such as biphenol or dicyandiamide, is not particularly limited, but is preferably 60 to 500.

[0115] The thermosetting agent (b2) contained in composition (III) and the film-like adhesive may be one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0116] The thermosetting agent (b2) is preferably a non-aromatic thermosetting agent that does not have an aromatic cyclic group, and more preferably a dicyandiamide, acid anhydride, amine, or thiol.

[0117] When using a thermosetting component (b), the content of the thermosetting agent (b2) in composition (III) and the film-like adhesive is preferably 0.5 to 10 parts by mass per 100 parts by mass of epoxy resin (b1), for example, it may be 0.5 to 5 parts by mass or 0.5 to 3 parts by mass. When the content of the thermosetting agent (b2) is above the lower limit, the thermosetting of the film-like adhesive proceeds more easily. When the content of the thermosetting agent (b2) is below the upper limit, the moisture absorption rate of the film-like adhesive is reduced, and the reliability of the package obtained using the film-like adhesive is further improved.

[0118] When using a thermosetting component (b), the content of the thermosetting component (b) in composition (III) and the film-like adhesive (for example, the total content of epoxy resin (b1) and thermosetting agent (b2)) is preferably 100 to 1000 parts by mass, more preferably 200 to 1000 parts by mass, per 100 parts by mass of acrylic resin (a1). For example, it may be any of 200 to 930 parts by mass, 200 to 890 parts by mass, and 200 to 800 parts by mass, or any of 300 to 1000 parts by mass, 300 to 1000 parts by mass, and 300 to 1000 parts by mass, or any of 300 to 930 parts by mass and 300 to 890 parts by mass. Having the content of the thermosetting component (b) within this range makes it easier to adjust the adhesive strength between the film-like adhesive and the support sheet described later.

[0119] When using a thermosetting agent (b2), the ratio of the content of the non-aromatic thermosetting agent to the content of the thermosetting agent (b2) in composition (III) and the film adhesive is preferably 70% by mass or more, and may be, for example, 80% by mass or more, 90% by mass or more, or 95% by mass or more. The higher the ratio, the greater the effect obtained by using the non-aromatic thermosetting agent. On the other hand, the aforementioned ratio is 100% by mass or less. In one embodiment, the proportion may be, for example, 70-100% by mass, 80-100% by mass, 90-100% by mass, and 95-100% by mass. However, these are just examples of the proportion.

[0120] <Compounds having at least two radical-reactive groups (c)> When a film-like adhesive containing compound (c) having at least two radical-reactive groups is irradiated with plasma, the radical-reactive groups of compound (c) become radicals due to the influence of the plasma radicals, causing a chain reaction. This allows the film-like adhesive to become a brittle cured material, which can then be more easily dry-etched, thus increasing the etching rate. Compound (c) having at least two radical-reactive groups is a low molecular weight compound having at least two radical-reactive groups, or an oligomer or polymer having at least two radical-reactive groups. The compound (c) having at least two radical-reactive groups is preferably further energy-ray curable.

[0121] Examples of compounds (c) having at least two radical-reactive groups include compounds having at least two polymerizable double bonds in the molecule, and acrylate compounds having at least two (meth)acryloyl groups are preferred. Acrylate compounds having at least two (meth)acryloyl groups are energy ray curable.

[0122] Examples of the aforementioned acrylate compounds include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. Examples include (meth)acrylates containing a chain-like aliphatic skeleton; cyclic aliphatic skeleton-containing (meth)acrylates such as dicyclopentanyl di(meth)acrylate and tricyclodecane dimethylol diacrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylates; urethane (meth)acrylate oligomers; epoxy-modified (meth)acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; and itaconic acid oligomers.

[0123] The weight-average molecular weight of compound (c) having at least two radical-reactive groups is preferably 100 to 30,000, more preferably 200 to 20,000, and even more preferably 300 to 10,000.

[0124] The compound (c) having at least two radical-reactive groups contained in composition (III) may be one or two or more, and if there are two or more, their combination and ratio can be arbitrarily selected.

[0125] In the film-like adhesive, the proportion of compound (c) having at least two radical-reactive groups relative to the total mass of the film-like adhesive is preferably 4% by mass or more, and more preferably 6% by mass or more. When the proportion is above the lower limit, the energy ray curing of the film-like adhesive becomes easier. On the other hand, the aforementioned ratio is preferably 20% by mass or less, and more preferably 10% by mass or less, in that it suppresses the excessive use of compound (c) having at least two radical reactive groups and can reduce manufacturing costs. In one embodiment, the proportion may be, for example, 4 to 20% by mass and 6 to 10% by mass. However, these are just examples of the proportions.

[0126] <Photopolymerization initiator (d)> Composition (III) and the film-like adhesive contain a photopolymerization initiator (d), which allows the polymerization reaction of compound (c), having at least two radical-reactive groups, to proceed efficiently when the compound (c) is energy-ray curable.

[0127] Examples of the photopolymerization initiator (d) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one; and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl Examples include acylphosphine oxide compounds such as diphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone; and quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.

[0128] The photopolymerization initiator (d) contained in composition (III) and the film-like adhesive may be one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0129] The boiling point of the photopolymerization initiator (d) is preferably 300°C or higher, and more preferably 400°C or higher. A higher boiling point of the photopolymerization initiator (d) makes it more difficult to gasify under reduced pressure conditions when dry etching the film-like adhesive, thus shortening the time required to maintain reduced pressure conditions when dry etching with plasma.

[0130] When a photopolymerization initiator (d) is used, the content of the photopolymerization initiator (d) in composition (III) and the film-like adhesive is preferably 0.1 to 50 parts by mass, more preferably 0.3 to 9 parts by mass, and particularly preferably 0.5 to 6 parts by mass, based on 100 parts by mass of the content of compound (c) having at least two radical reactive groups.

[0131] <Curing accelerator (e)> Curing accelerator (e) is an ingredient used to adjust the thermal curing rate of the film-type adhesive. Preferred curing accelerators (e) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms); organophosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; and inclusion compounds using the aforementioned imidazoles as guest compounds.

[0132] The curing accelerator (e) contained in composition (III) and the film-like adhesive may consist of only one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0133] When a curing accelerator (e) is used, the content of the curing accelerator (e) in composition (III) and the film adhesive is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the content of the thermosetting component (b) (for example, the total content of epoxy resin (b1) and thermosetting agent (b2)). When the content of the curing accelerator (e) is above the lower limit, the effect of using the curing accelerator (e) is more pronounced. When the content of the curing accelerator (e) is below the upper limit, for example, the effect of suppressing the migration and segregation of a highly polar curing accelerator (e) to the adhesive interface side with the adherend in the film adhesive under high temperature and high humidity conditions is enhanced, and the reliability of the package obtained using the film adhesive is further improved.

[0134] ○Other ingredients The adhesive composition may contain, or may not contain, any other component that does not fall under any of the following categories: acrylic resin (a1), thermosetting component (b), compound having at least two radical-reactive groups (c), photopolymerization initiator (d), or curing accelerator (e). Examples of the other components mentioned above include fillers (f), coupling agents (g), crosslinking agents (h), colorants (i), and general-purpose additives (j). The other components contained in composition (III) and the film-like adhesive, such as fillers (f), coupling agents (g), crosslinking agents (h), colorants (i), and general-purpose additives (j), may consist of only one type or two or more types, and if there are two or more types, their combinations and ratios can be arbitrarily selected.

[0135] <Filling material (f)> By including a filler (f) in the film-type adhesive, the coefficient of thermal expansion can be easily adjusted. Optimizing this coefficient of thermal expansion for the object to which the film-type adhesive is applied further improves the reliability of the package obtained using the film-type adhesive. Furthermore, the inclusion of filler (f) in the film-type adhesive suppresses volume changes due to temperature fluctuations in the cured film-type adhesive, thereby reducing moisture absorption and improving heat dissipation.

[0136] The filler (f) may be either an organic filler or an inorganic filler, but an inorganic filler is preferred. Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, and boron nitride; beads formed from these inorganic fillers in a spherical shape; surface-modified products of these inorganic fillers; single-crystal fibers of these inorganic fillers; and glass fibers. Among these, the inorganic filler is preferably silica, alumina, or a surface-modified version thereof.

[0137] The average particle size of the filler (f) is not particularly limited, but is preferably between 10 nm and 5 μm. Having the average particle size of the filler (f) within this range allows for the full utilization of the effects of using the filler (f) and further enhances the storage stability of the film-like adhesive.

[0138] In this specification, "average particle diameter" refers to the particle diameter at 50% of the integrated value in the particle size distribution curve obtained by laser diffraction scattering (D 50 This refers to the value of ).

[0139] In the film-like adhesive, the ratio of the filler (f) content to the total mass of the film-like adhesive is preferably less than 15% by mass, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. As will be described later, when the film-like adhesive is cut by irradiating it with plasma, having the ratio within this range makes it easier to cut. On the other hand, the aforementioned ratio is 0% by mass or more. To facilitate the improvement of the etching rate when cutting the film-like adhesive by irradiating it with plasma, it is most preferable that the proportion is 0% by mass, that is, that the film-like adhesive does not contain filler (f).

[0140] <Coupling agent (g)> The film-type adhesive exhibits improved adhesion and bonding to the substrate by containing a coupling agent (g). Furthermore, the inclusion of the coupling agent (g) in the film-type adhesive improves the water resistance of the cured product without compromising its heat resistance. The coupling agent (g) has a functional group capable of reacting with inorganic or organic compounds.

[0141] The coupling agent (g) is preferably a compound having a functional group that can react with a functional group (e.g., a second functional group) of an acrylic resin (a1), a thermosetting component (b), etc., and is more preferably a silane coupling agent.

[0142] Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane (also known as 3-glycidoxypropyltrimethoxysilane; the same applies to other compounds hereafter), 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-(2-aminoethylamino)propyltrimethoxy Examples include sisilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfan, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, oligomeric or polymeric organosiloxanes, etc.

[0143] When a coupling agent (g) is used, the content of the coupling agent (g) in composition (III) and the film adhesive is preferably 0.03 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and may be, for example, 0.1 to 1 part by mass, based on 100 parts by mass of the total content of the acrylic resin (a1) and the thermosetting component (b). When the content of the coupling agent (g) is above the lower limit, the effects of using the coupling agent (g), such as improved dispersibility of the filler (f) in the resin and improved adhesion of the film adhesive to the adherend, are more pronounced. When the content of the coupling agent (g) is below the upper limit, outgassing is further suppressed.

[0144] <Crosslinking agent (h)> When using an acrylic resin (a1) having functional groups such as vinyl groups, (meth)acryloyl groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can bond with other compounds, composition (III) and the film adhesive may contain a crosslinking agent (h) for crosslinking the functional groups with other compounds. By crosslinking with the crosslinking agent (h), the initial adhesive strength and cohesive strength of the film adhesive can be adjusted.

[0145] Examples of crosslinking agents (h) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking agents (crosslinking agents having an aziridinyl group).

[0146] In composition (III) and the film-like adhesive, the content of the crosslinking agent (h) is preferably 6 parts by mass or less, more preferably 3 parts by mass or less, and on the other hand, 0 parts by mass or more, based on the content of acrylic resin (a1) per 100 parts by mass. The lower the content of the crosslinking agent (h), the higher the pickability of the workpiece with the film-like adhesive or the workpiece with the cured adhesive tends to be, and it is particularly preferable that the film-like adhesive does not contain the crosslinking agent (h).

[0147] <Coloring agent (i)> The coloring agent (i) is a component in the film-like adhesive and its cured product that can adjust the transmittance of light of various wavelengths. Examples of colorants (i) include known ones such as inorganic pigments, organic pigments, and organic dyes.

[0148] When a coloring agent (i) is used, the ratio of the coloring agent (i) content to the total mass of the film adhesive is preferably 0.01 to 10% by mass, regardless of the type of coloring agent (i). When the ratio is above the lower limit, the effect of using the coloring agent (i) is more pronounced. When the ratio is below the upper limit, excessive use of the coloring agent (i) is suppressed.

[0149] <General-purpose additive (j)> The general-purpose additive (j) may be any known additive and can be arbitrarily selected depending on the purpose, and is not particularly limited. Examples of the general-purpose additive (j) include ultraviolet absorbers, plasticizers, antistatic agents, antioxidants (sometimes referred to as "antioxidant (j1)" in this specification), gettering agents, defoaming agents, leveling agents, and the like.

[0150] Examples of antioxidants (j1) include radical scavengers and light stabilizers, among which hindered amine-based light stabilizers are preferred. Specifically, examples include mixed esters of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0151] The content of composition (III) and the general-purpose additive (i) in the film-like adhesive is not particularly limited and can be appropriately selected depending on the type of general-purpose additive (i), for example.

[0152] In terms of improving the pickability of workpieces with film-like adhesive or workpieces with cured adhesive, the ratio of antioxidant (j1) content to the total mass of the film-like adhesive is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 3.0% by mass or less. On the other hand, the above proportion is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more.

[0153] <Solvent> Composition (III) preferably further contains a solvent. Composition (III) containing a solvent has good handling properties.

[0154] In this specification, unless otherwise specified, the term "solvent" includes not only substances that dissolve the target component but also dispersion media that disperse the target component.

[0155] The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; and amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. The solvent contained in composition (III) may be one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0156] The solvent contained in composition (III) is preferably methyl ethyl ketone or the like, as this allows for more uniform mixing of the components contained in composition (III).

[0157] The solvent content of composition (III) is not particularly limited and may be appropriately selected depending on the type of components other than the solvent.

[0158] <<Method for manufacturing adhesive composition>> An adhesive composition (for example, composition (III)) is obtained by blending the components that constitute it. There are no particular restrictions on the order in which each component is added during formulation, and two or more components may be added simultaneously. When using a solvent, the solvent may be mixed with any of the other components to pre-dilute the mixture, or the solvent may be mixed with the other components without pre-diluting them.

[0159] The method of mixing each component during formulation is not particularly limited; it can be appropriately selected from known methods such as mixing by rotating a stirring bar or impeller, mixing using a mixer, or mixing by applying ultrasonic waves. The temperature and time during the addition and mixing of each component are not particularly limited as long as the components do not deteriorate, and can be adjusted as appropriate, but a temperature of 15 to 30°C is preferred.

[0160] ◇Film-type adhesive composite sheet A film-like adhesive composite sheet according to one embodiment of the present invention comprises a support sheet and a film-like adhesive provided on one surface of the support sheet, wherein the film-like adhesive is the film-like adhesive according to the above-described embodiment of the present invention. The film-like adhesive composite sheet of this embodiment can be used, for example, as a sheet for cutting a film-like adhesive that has been attached to a workpiece by plasma irradiation. In either case, the workpiece with the film-like adhesive or the workpiece with the cured adhesive obtained after plasma irradiation is ultimately pulled away from the support sheet and picked up.

[0161] In the film-like adhesive composite sheet of this embodiment, since the film-like adhesive contains a compound (c) having at least two radical-reactive groups, when plasma is irradiated from the side of the multiple workpieces onto the film-like adhesive exposed between the multiple workpieces, the etching rate of the film-like adhesive can be increased.

[0162] <<Support Sheet>> The support sheet may consist of one layer (single layer) or of two or more layers. If the support sheet consists of multiple layers, the constituent materials and thicknesses of these layers may be the same or different, and the combination of these layers is not particularly limited as long as it does not impair the effects of the present invention.

[0163] Examples of the support sheet include one consisting only of a base material; one comprising a base material and an adhesive layer provided on one surface of the base material; and one constructed by laminating a base material, an adhesive layer, and an intermediate release layer in this order in the thickness direction.

[0164] If the support sheet comprises the base material and the adhesive layer, in the film-like adhesive composite sheet, the adhesive layer is positioned between the base material and the film-like adhesive. If the support sheet comprises the base material, adhesive layer, and intermediate release layer, then in the film-like adhesive composite sheet, the adhesive layer and intermediate release layer are arranged between the base material and the film-like adhesive. The adhesive layer and the intermediate release layer are layers designed to facilitate the pickup of the workpiece with the cured adhesive, which will be described later, from the support sheet.

[0165] The aforementioned film-like adhesive composite sheet is used by attaching the side of the film-like adhesive opposite to the support sheet side (for example, the first side) to the workpiece or workpiece. For example, if the workpiece is a semiconductor wafer, the film-like adhesive composite sheet is used by attaching the film-like adhesive within it to the back surface of the semiconductor wafer or semiconductor chip.

[0166] When a support sheet consisting only of the base material is used, a film-like adhesive composite sheet can be manufactured at low cost. When a support sheet comprising a base material and an adhesive layer is used, the adhesive strength between the support sheet (more specifically, the adhesive layer) and the film-like adhesive in the film-like adhesive composite sheet can be easily adjusted. Furthermore, when a support sheet consisting only of a base material is used, it is necessary to separately provide an adhesive layer for the fixture on the base material when fixing the film-like adhesive composite sheet to a fixing jig such as a ring frame. However, when a support sheet comprising a base material and an adhesive layer is used, the film-like adhesive composite sheet can be fixed to the fixing jig by the adhesive layer, thus eliminating the need for the adhesive layer for the fixture.

[0167] The aforementioned film-like adhesive composite sheet may further include a release film on the side of the film-like adhesive opposite to the support sheet side (for example, the first side).

[0168] The following describes the configuration of the film-like adhesive composite sheet of this embodiment for each type of support sheet.

[0169] Figure 3 is a schematic cross-sectional view showing an example of a film-like adhesive composite sheet according to this embodiment. In Figures 3 and beyond, components identical to those shown in previously explained figures are denoted by the same reference numerals, and their detailed explanations are omitted.

[0170] The film-like adhesive composite sheet 101 shown in Figure 3 comprises a support sheet 10 and a film-like adhesive 13 provided on one surface (sometimes referred to as the "first surface" in this specification) 10a of the support sheet 10. The film-like adhesive 13 is the film-like adhesive 13 shown in Figure 2.

[0171] The support sheet 10 consists only of the base material 11, and one side (first side) 10a of the support sheet 10 is the same as one side 11a of the base material 11. The other side (the side opposite to the film-like adhesive 13) 10b of the support sheet 10 is the same as the other side 11b of the base material 11.

[0172] In the film-like adhesive composite sheet 101, a jig adhesive layer 16 is provided in the region near the peripheral edge of the film-like adhesive 13 (a region with an annular planar shape along the peripheral edge) of the first surface 13a of the film-like adhesive 13 that is opposite to the support sheet 10 side.

[0173] The film-like adhesive composite sheet 101 further includes a release film 15 in the area of ​​the first surface 13a of the film-like adhesive 13 where the jig adhesive layer 16 is not provided. The release film 15 is further provided on the jig adhesive layer 16 in the area near the peripheral edge of the film-like adhesive 13. In the film-like adhesive composite sheet 101, the release film 15 has any configuration.

[0174] The film-like adhesive composite sheet 101 is used by attaching a workpiece or workpiece compound to the first surface 13a of the film-like adhesive 13 after the release film 15 has been removed. The side of the jig adhesive layer 16 opposite to the film-like adhesive 13 is attached to the fixing jig.

[0175] The film-like adhesive composite sheets of this embodiment are not limited to those shown in Figure 3, and for example, some components of these film-like adhesive composite sheets may be modified, deleted, or added without departing from the spirit of the present invention.

[0176] Next, each layer constituting the film-like adhesive composite sheet of this embodiment will be described in more detail.

[0177] <Base material> The substrate may be in the form of a sheet or a film, and may be one of known types. Examples of constituent materials for the base material include various resins. Examples of the aforementioned resins include polyolefins such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and polypropylene; ethylene-based copolymers such as ethylene-vinyl acetate copolymer and ethylene-(meth)acrylic acid copolymer (polymers obtained using ethylene as a monomer); vinyl chloride resins (resins obtained using vinyl chloride as a monomer); polyester; and polyimide. Examples of the aforementioned resins include crosslinked resins obtained by crosslinking one or more of the aforementioned resins exemplified so far; and modified resins such as ionomers using one or more of the aforementioned resins exemplified so far.

[0178] The resin constituting the base material may consist of only one type, or two or more types. If there are two or more types, their combination and ratio can be arbitrarily selected.

[0179] The base material may consist of one layer (single layer) or of two or more layers. If it consists of multiple layers, these layers may be identical or different, and there are no particular limitations on the combination of these layers.

[0180] The thickness of the substrate is preferably 50 to 300 μm, and more preferably 60 to 140 μm. Having the substrate thickness within this range improves the flexibility of the film-like adhesive composite sheet and its suitability for adhesion to the workpiece. Here, "substrate thickness" refers to the total thickness of the substrate. For example, the thickness of a substrate consisting of multiple layers refers to the total thickness of all the layers that make up the substrate.

[0181] In addition to the main constituent materials such as the aforementioned resin, the base material may also contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and plasticizers.

[0182] The substrate may be transparent or opaque, and may be colored or have other layers deposited on it, depending on the purpose. The substrate is preferably one that allows energy rays to pass through.

[0183] The substrate may or may not have its surface treated with sandblasting, solvent treatment, or other surface treatments to adjust its adhesion to the layer provided thereon (for example, a film-like adhesive, an adhesive layer, or the aforementioned other layer); oxidation treatments such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, or hot air treatment; lipophilic treatment; or hydrophilic treatment. Furthermore, the substrate's surface may or may not be treated with a primer.

[0184] The base material may contain components within a specific range (e.g., resin, etc.) to have adhesive properties on at least one surface.

[0185] The substrate can be manufactured by known methods. For example, a substrate containing a resin can be manufactured by molding a resin composition containing the resin.

[0186] <Adhesive layer> The adhesive layer is in the form of a sheet or film and contains an adhesive. The adhesive layer may be of known type. Examples of the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin.

[0187] The adhesive layer may consist of one layer (single layer) or of two or more layers. If it consists of multiple layers, these layers may be identical or different, and there are no particular limitations on the combination of these layers.

[0188] The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 100 μm, and may be, for example, 1 to 60 μm or 1 to 30 μm. Here, "thickness of the adhesive layer" refers to the total thickness of the adhesive layer. For example, the thickness of an adhesive layer consisting of multiple layers refers to the total thickness of all the layers that make up the adhesive layer.

[0189] The adhesive layer may be transparent or opaque, and may be colored depending on the purpose. The adhesive layer is preferably one that allows energy rays to pass through.

[0190] The adhesive layer may be either energy-ray curable or non-energy-ray curable. The physical properties of the energy-ray curable adhesive layer can be adjusted before and after curing. For example, by curing the energy-ray curable adhesive layer before picking up the workpiece with the cured adhesive (described later), the workpiece with the cured adhesive can be picked up more easily from the support sheet.

[0191] An adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive layer can be formed on the desired area by applying the adhesive composition to the surface on which the adhesive layer is to be formed and drying it as needed. The ratio of components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of those components in the adhesive layer.

[0192] The coating and drying of the adhesive composition can be carried out, for example, in the same manner as in the coating and drying of the adhesive composition described above.

[0193] When the adhesive layer is energy ray curable, examples of energy ray curable adhesive compositions include: an adhesive composition (I-1) containing a non-energy ray curable adhesive resin (I-1a) and an energy ray curable compound; an adhesive composition (I-2) containing an energy ray curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray curable adhesive resin (I-1a); and an adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

[0194] When the adhesive layer is non-energy ray curable, examples of non-energy ray curable adhesive compositions include adhesive compositions (I-4) containing the non-energy ray curable adhesive resin (I-1a).

[0195] <Release film> The aforementioned release film is the same as the first release film or second release film (first release film 151 or second release film 152 shown in Figure 2).

[0196] <Adhesive layer for jigs> The adhesive layer for the jig may be of known origin. The adhesive layer for the jig may be, for example, a single-layer structure containing adhesive components, or a multi-layer structure in which layers containing adhesive components are laminated on both sides of a core sheet.

[0197] <Other layers> The film-like adhesive composite sheet of this embodiment may or may not have any other layers at any location that do not fall under any of the following categories: the base material, the adhesive layer, the intermediate release layer, the film-like adhesive, the release film, or the jig adhesive layer. The aforementioned other layers can be arbitrarily selected depending on the purpose and are not particularly limited.

[0198] The aforementioned other layer may consist of one layer (single layer) or of two or more layers. If it consists of multiple layers, these layers may be identical or different from each other, and the combination of these layers is not particularly limited.

[0199] The thickness of the other layer can be arbitrarily selected depending on the type of the other layer, and is not particularly limited.

[0200] In this embodiment, it is preferable that the film-like adhesive composite sheet does not have any other layers between the support sheet and the film-like adhesive. By using such a film-like adhesive composite sheet, the pickability of workpieces with film-like adhesive or workpieces with cured adhesive is further improved.

[0201] ◇Method of manufacturing a film-like adhesive composite sheet The film-like adhesive composite sheet of this embodiment can be manufactured by laminating the above-mentioned layers in corresponding positional relationships and, if necessary, adjusting the shape of some or all of the layers. The method for forming each layer is as described above.

[0202] For example, when laminating a film-like adhesive onto a support sheet, the above-mentioned adhesive composition can be applied to the support sheet and dried as needed. Alternatively, a film-like adhesive can be laminated onto a support sheet by applying an adhesive composition to the release film and drying it as needed to form a film-like adhesive on the release film, and then bonding the exposed surface of this film-like adhesive to one side of the support sheet. In this case, it is preferable to apply the adhesive composition to the release-treated surface of the release film.

[0203] Up to this point, we have given examples of cases where a film-like adhesive is laminated onto a substrate, but the above method can also be applied, for example, when laminating an adhesive layer onto a substrate when manufacturing a support sheet. When laminating an adhesive layer, the adhesive composition described above is used.

[0204] For example, when laminating a new layer (hereinafter abbreviated as "second layer") on top of the uppermost layer (hereinafter abbreviated as "first layer") already laminated on a substrate, the second layer can be formed in advance on a release film using the composition for forming the second layer, and the exposed surface of the formed second layer opposite to the side in contact with the release film can be bonded to the exposed surface of the first layer on the substrate to form a continuous two-layer laminated structure (in other words, a laminated structure of the first and second layers). In this case, it is preferable to coat the release treatment surface of the release film with the composition. If the second layer is the film-like adhesive, the adhesive composition is used as the composition for forming the second layer. The release film may be removed as needed after the formation of the laminated structure. Alternatively, one of the release films may not be removed after the formation of the laminated structure and may be used as the outermost release film in the film-like adhesive composite sheet (for example, the release film 15 shown in Figure 3).

[0205] <<Modified Method of Manufacturing a Workpiece with Film-Like Adhesive>> The method for manufacturing a workpiece with a film-like adhesive coating may include, or may not include, other steps that do not fall under any of the above categories, as long as they do not impair the effects of the present invention. The aforementioned other steps can be arbitrarily selected depending on the purpose, and can also be arbitrarily selected depending on the type of film-like adhesive composite sheet or workpiece, and are not particularly limited. The timing for performing the other processes can be appropriately selected depending on the content of those other processes.

[0206] Up to this point, we have described the manufacturing method using the film-like adhesive composite sheet 101 shown in Figure 3. However, in the manufacturing method of the film-like adhesive-coated workpiece of this embodiment, other film-like adhesive composite sheets may also be used. When using the aforementioned other film-like adhesive composite sheets, the method for manufacturing a workpiece with film-like adhesive according to this embodiment may have one or more of the aforementioned other steps, performed at any given time, based on the differences in the configuration between the aforementioned other film-like adhesive composite sheets and the film-like adhesive composite sheet 101 shown in Figure 3.

[0207] <<Modified Method of Manufacturing a Workpiece with Cured Adhesive>> The method for manufacturing a workpiece with a cured adhesive coating may include, or may not include, other steps that do not fall under any of the above categories, as long as they do not impair the effects of the present invention. The aforementioned other steps can be arbitrarily selected depending on the purpose, and can also be arbitrarily selected depending on the type of film-like adhesive composite sheet or workpiece, and are not particularly limited. The timing for performing the other processes can be appropriately selected depending on the content of those other processes.

[0208] Up to this point, we have described the manufacturing method using the film-like adhesive composite sheet 101 shown in Figure 3. However, in the manufacturing method of the adhesive-cured workpiece of this embodiment, other film-like adhesive composite sheets may also be used. When using the aforementioned other film-like adhesive composite sheets, the method for manufacturing the adhesive-cured workpiece according to this embodiment may have one or more of the aforementioned other steps, performed at any given time, based on the differences in the configuration between the aforementioned other film-like adhesive composite sheets and the film-like adhesive composite sheet 101 shown in Figure 3.

[0209] ◇Manufacturing method for substrate devices (Method of using workpieces with film-like adhesive or workpieces with cured adhesive) A substrate device can be manufactured using a workpiece with a film-like adhesive or a workpiece with a cured adhesive obtained by the manufacturing method described above. The substrate device can be manufactured by known methods, except that it uses a workpiece with the aforementioned film-like adhesive or a workpiece with a cured adhesive. For example, a workpiece with a film-like adhesive or a workpiece with a cured adhesive can be attached to a circuit board by bonding it to the circuit board using the film-like adhesive or cured adhesive (energy-ray cured film-like adhesive) (mounting process). If the film-like adhesive is thermosetting, the workpiece can be firmly fixed to the circuit board by further thermosetting the energy-ray cured film-like adhesive or the film-like adhesive after mounting. The energy-ray cured film-like adhesive or the film-like adhesive may also be thermoset simultaneously by heating when the workpiece is sealed with resin on the circuit board. In addition to mounting the workpiece onto the circuit board, the desired circuit board device can be manufactured by adding other processes as needed. [Examples]

[0210] The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited in any way to the examples shown below.

[0211] <<Raw materials for resin manufacturing>> The full names of the resin manufacturing raw materials, which are abbreviated in this example and comparative example, are shown below. MA: Methyl acrylate HEA: 2-hydroxyethyl acrylate EA: Ethyl acrylate BA: n-butyl acrylate iBA: Isobutyl Acrylate tBA: tert-butyl acrylate LA: Lauryl acrylate

[0212] <<Raw materials for manufacturing adhesive compositions>> The raw materials used in the manufacture of the adhesive composition are listed below. [Acrylic resin (a1)] (a)-1: Acrylic resin obtained by copolymerizing MA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 500,000, glass transition temperature 5.9°C). (a)-2: Acrylic resin obtained by copolymerizing EA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 500,000, glass transition temperature -22.7°C). (a)-3: Acrylic resin obtained by copolymerizing BA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 500,000, glass transition temperature -48.9°C). (a)-4: Acrylic resin obtained by copolymerizing iBA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 500,000, glass transition temperature -21.0°C). (a)-5: Acrylic resin obtained by copolymerizing tBA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 500,000, glass transition temperature 32.7°C). (a)-6: Acrylic resin obtained by copolymerizing LA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 500,000, glass transition temperature -27.9°C). (a)-7: Acrylic resin obtained by copolymerizing BA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 800,000, glass transition temperature -48.9°C). (a)-8: Acrylic resin obtained by copolymerizing BA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 300,000, glass transition temperature -48.9°C). (a)-9: Acrylic resin obtained by copolymerizing BA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 100,000, glass transition temperature -48.9°C). [Epoxy resin (b1)] (b1)-1: Mixture of liquid bisphenol F type epoxy resin and acrylic rubber fine particles (Nippon Shokubai Co., Ltd. "Acryset (registered trademark) BPF307", epoxy equivalent 235 g / eq) (b1)-2: Dicyclopentadiene type epoxy resin (XD-1000, manufactured by Nippon Kayaku Co., Ltd., softening point 68-78°C, epoxy equivalent 245-260 g / eq) [Thermosetting agent (b2)] (b2)-1: Dicyandiamide (ADEKA Hardener® EH-3636AS, manufactured by ADEKA Corporation, solid dispersion latent curing agent, softening point 209°C, hydroxyl group equivalent 21 g / eq) [Compounds having at least two radical-reactive groups (c)] (c)-1: Tricyclodecanedimethylol diacrylate (manufactured by Nippon Kayaku Co., Ltd., "KAYARAD® R-684", molecular weight 304) [Photopolymerization initiator (d)] (d)-1:1-Hydroxycyclohexylphenyl ketone (Omnirad® 184, manufactured by IGM RESINS BV, boiling point: 175°C) (d)-2: 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one (Omnirad® 127, manufactured by IGM RESINS BV, boiling point: 525°C) [Curing accelerator (e)] (e)-1:2-Phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemicals Corporation, "Curezol (registered trademark) 2PHZ-PW") [Coupling agent (g)] (g)-1: Silicate compound added with 3-glycidoxypropyltrimethoxysilane (manufactured by Mitsubishi Chemical Corporation, "MKC (registered trademark) Silicate MSEP-2") [Antioxidant (j1)] (j1)-1: Mixed esterified product of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (manufactured by ADEKA Corporation, "ADEKA STAB (registered trademark) LA-63P", hindered amine light stabilizer (HALS))

[0213] [Example 1] <<Manufacture of film adhesive>> <Manufacture of adhesive composition> The components shown in Table 1 were dissolved or dispersed in methyl ethyl ketone so as to have the contents shown in Table 1, and stirred at 23°C to produce a thermosetting adhesive composition in which the total concentration of all components other than the solvent was 50% by mass.

[0214] The description "-" in the column of "Contained component (content (parts by mass))" in Table 1 means that the film adhesive does not contain that component. This is the same in other tables.

[0215] <Manufacture of film adhesive> Using a release film (second release film, "SP-PET502150" manufactured by Lintec Corporation, thickness 50 μm) with one side of a polyethylene terephthalate film being subjected to a release treatment by silicone treatment, the adhesive composition obtained above was applied to the release-treated surface and dried at 100°C for 1 minute, thereby producing a film-shaped adhesive having both energy ray curability and thermosetting properties with a thickness of 20 μm. Hereinafter, in this specification, these film-shaped adhesives may be referred to as "film-shaped adhesive (F1)". Furthermore, by laminating the release-treated surface of a separate release film (first release film, "SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) onto the exposed surface of the obtained film-shaped adhesive (film-shaped adhesive (F1)) on the side without the second release film, a film-shaped adhesive with a release film according to Example 1 was manufactured, which is composed of a film-shaped adhesive, a first release film provided on one surface of the film-shaped adhesive, and a second release film provided on the other surface of the film-shaped adhesive.

[0216] <<Evaluation of Film-shaped Adhesive>> <Measurement of Etching Rate (O2 Gas Plasma Irradiation) of Film-shaped Adhesive> A silicon chip (size: 30 mm × 30 mm, thickness: 300 μm) was fabricated from a silicon wafer whose back surface was ground with a #2000 wheel. The first release film was removed from the 20-μm-thick film-shaped adhesive obtained above, and the exposed surface of the resulting film-shaped adhesive was attached to the ground surface of the silicon chip obtained above. Further, by cutting and removing the region of the film-shaped adhesive that protruded from the silicon chip after attachment, a silicon chip with a film-shaped adhesive with a release film was simply fabricated, in which a film-shaped adhesive having the same size as the ground surface was attached to the entire ground surface of the silicon chip.

[0217] Hereinafter, the etching rate of the film-shaped adhesive when irradiated with plasma using O2 gas was measured by the method described above with reference to FIG. 4. More specifically, a test specimen was prepared by removing the second release film from the film-like adhesive-coated silicon chip obtained above, and then applying a polyimide-based adhesive tape (10 mm wide strip) to a strip-shaped region of the exposed surface of the film-like adhesive that was parallel to one pair of opposing sides and connecting the other pair of opposing sides, thereby forming a strip-shaped mask on the exposed surface of the film-like adhesive. Next, a dry etching apparatus (Samco RIE apparatus) was used as the plasma irradiation device, and the test specimen was irradiated with plasma from the side of the film-like adhesive. At this time, O2 gas was used, with an O2 gas flow rate (sccm) / argon gas flow rate (sccm) ratio of 50 / 3, and the plasma was irradiated under reduced pressure conditions of 20 Pa, with an RF (Radio Frequency) power of 250 W and a processing time of 5 min. As a result, the areas of the film-like adhesive that were not covered by adhesive tape (not masked) were etched.

[0218] After plasma irradiation (etching), the test piece was removed from the plasma irradiation device, the adhesive tape was removed, and the surface roughness of the film adhesive side of the film adhesive-coated silicon chip was measured using a contact surface roughness meter (Mitutoyo SV-3000S4). This allowed for the measurement of the height difference (etching distance L) between the original first surface of the film adhesive and the etched area of ​​the film adhesive. The etching rate was then calculated from this measurement and the plasma irradiation time (etching time), and this was adopted as the etching rate of the film adhesive in Example 1. The results are shown in Table 1.

[0219] <<Manufacturing and Evaluation of Film-Type Adhesives>> [Examples 2 to 17 and Comparative Example 1] Except for changing the type of components in the adhesive composition, or the type and amount of components, so that the types and amounts of components in the film adhesive are as shown in Tables 1 to 5, the film adhesives with release films (film adhesives with a thickness of 20 μm) of Examples 2 to 17 and Comparative Example 1 were manufactured using the same method as in Example 1. In addition, in Examples 2 to 17 and Comparative Example 1, the notation "-" in the "Contained Components (Content (parts by mass))" column for the film-like adhesive means that the film-like adhesive does not contain that component. Furthermore, for the film-like adhesives (with a thickness of 20 μm) of Examples 2 to 10, the etching rate of the film-like adhesives was measured when irradiated with plasma using O2 gas, in the same manner as in Example 1. The results are shown in Tables 1 to 5.

[0220] <<Manufacturing of film-like adhesive composite sheets>> [Example 1-1] The first release film was removed from the film-like adhesive with a release film (film-like adhesive with a thickness of 20 μm) obtained in Example 1 above. The film-like adhesive composite sheet of Example 1-1 was manufactured by using a support sheet 10 (a support sheet 10 consisting only of the base material 11) (thickness 80 μm) and laminating the exposed side of the film-like adhesive opposite to the side with the second release film to one side of the support sheet 10. This film-like adhesive composite sheet is a film-like adhesive composite sheet with a release film, constructed by laminating a support sheet consisting only of the base material, a film-like adhesive, and a second release film in this order in the thickness direction. Here, the support sheet 10 has a single-layer structure of linear low-density polyethylene layers.

[0221] [Examples 2-1 to 17-1 and Comparative Example 1-1] The film-like adhesive composite sheets of Examples 2-1 to 17-1 and Comparative Example 1-1 were manufactured in the same manner as in Example 1-1, except that the film-like adhesive with a release film (film-like adhesive with a thickness of 20 μm) of Example 1 was replaced with the film-like adhesive with a release film (film-like adhesive with a thickness of 20 μm) of Examples 2 to 17.

[0222] [Examples 1-2] (Fabrication of silicon chip array holders) Using a half-cut dicer (DISCO "DFG6363"), half-cuts were performed on the silicon wafer, creating 20 μm wide grooves at 500 μm intervals in two perpendicular directions, extending from the surface of the wafer to a certain distance in the thickness direction. After half-cutting, a backgrind tape (Lintec Corporation's "Adwill E-3125KN") was applied to the grooved surface of the silicon wafer. The back surface of the silicon wafer was then ground using a polishing device (DISCO Corporation's "DFG8761"). Finally, the ground surface was dry-polished (finished thickness 50 μm) to create grooves on the ground surface of the silicon wafer. This allowed the silicon wafer to be divided at the grooved areas, and a group of silicon chips (500 μm × 500 μm × 50 μm) were fabricated.

[0223] In the film-like adhesive composite sheet of Example 1-1 obtained above, the second release film was removed, and the exposed surface of the film-like adhesive was collectively attached to the back surface (grinding surface) of the group of silicon chips (silicon chip group) obtained above. Then, using an ultraviolet irradiation device (Lintec Corporation "RAD2700"), an illuminance of 230 mW / cm² was applied. 2 , light intensity 500mJ / cm 2 Under these conditions, the adhesive layer within the backgrind tape was cured by irradiating it with ultraviolet light, and the backgrind tape was removed from the group of silicone chips. Based on the above, a silicon chip holder of Example 1-2 was fabricated, which is constructed by aligning and holding multiple silicon chips on the side of the film adhesive in the film adhesive composite sheet that is opposite to the side of the support sheet.

[0224] [Examples 1-3] (Fabrication of film-type adhesive-coated silicon chips (O2 gas plasma irradiation)) The silicon chip group holders of Examples 1-2 obtained above were subjected to a 5 × 10⁻¹⁰ plasma irradiation using a dry etching apparatus (Samco RIE apparatus) as the plasma irradiation device. ―5 After reducing the pressure to Pa, the ratio of the O2 gas flow rate (sccm) to the argon gas flow rate (sccm) was set to 50 / 3, and the pressure inside the apparatus was reduced to 20 Pa. Under this reduced pressure environment of 20 Pa, the O2 gas was plasma-generated at an RF (Radio Frequency) power of 250 W, and a 20 μm thick film-like adhesive was plasma-irradiated for 20 minutes. This produced the film-like adhesive-coated silicon chips of Examples 1-3, which consisted of a silicon chip and a pre-cut film-like adhesive provided on the back surface of the silicon chip. These multiple film-like adhesive-coated silicon chips were aligned and held on a support sheet 10, and together with the support sheet 10, they constituted a group of film-like adhesive-coated silicon chips. Also, at this time, 5 × 10 ―5 Table 1 shows the time (min) taken to reduce the pressure to Pa.

[0225] [Examples 2-2 to 17-2 and Comparative Example 1-2] (Fabrication of silicon chip array holders) In Example 1-2 described above, the silicon chip group holders of Examples 2-2 to 17-2 and Comparative Example 1-2 were manufactured in the same manner as in Example 1-2, except that the film-like adhesive composite sheet of Example 1-1 was replaced with the film-like adhesive composite sheet of Examples 2-1 to 17-1 and Comparative Example 1-1.

[0226] [Examples 2-3 to Examples 17-3 and Comparative Example 1-3] (Preparation of Silicon Chip with Film Adhesive (Irradiated with O2 Gas Plasma)) In Example 1-3 above, except that the silicon chip group retainer of Example 1-2 above was changed to the silicon chip group retainers of Examples 2-2 to Examples 17-2 and Comparative Example 1-2, silicon chips with film adhesives (irradiated with O2 gas plasma) of Examples 2-3 to Examples 17-3 and Comparative Example 1-3 were prepared in the same manner as in Example 1-3 above. Among these, for Examples 2-3 to Examples 8-3 and Comparative Example 1-3, the time (min) required to reduce the pressure to 5×10 ―5 Pa is shown in Tables 1 to 5.

[0227]

Table 1

[0228]

Table 2

[0229] [[ID=’28]]

Table 3

[0230]

Table 4

[0231] [[ID=’44]]

Table 5

[0232] As is clear from the above results, when the film-like adhesives of Examples 1 to 17 were cut by plasma irradiation, the etching rate was faster than in the conventional method. Since the film-like adhesives of Examples 1 to 17 contain compound (c) having at least two radical-reactive groups, when plasma is irradiated onto the exposed film-like adhesive, radicals are generated on the exposed portion of the film-like adhesive. As a result, the film-like adhesive hardens, making it possible to create a cured material that is more brittle than the film-like adhesive, and thus enabling a faster etching rate. On the other hand, when the film-like adhesive of Comparative Example 1 was cut by plasma irradiation, the etching rate could not be improved, and in Comparative Examples 1-3, the film-like adhesive layer was not completely cut. This is presumed to be because the film-like adhesive of Comparative Example 1 does not contain compound (c) having at least two radical-reactive groups, so the film-like adhesive in the exposed areas did not harden due to radicals from the plasma, and therefore the etching rate by plasma did not improve. [Industrial applicability]

[0233] This invention can be used in the manufacture of substrate devices. [Explanation of Symbols]

[0234] 10...Support sheet, 10a...First side of the support sheet 11...Base material 13...Film-type adhesive, 13a...First side of film-type adhesive 101...Film-like adhesive composite sheet 132…Adhesive cured product 133... Pre-cut film-type adhesive 134…Energy-ray cured product of film-type adhesive 90...semiconductor chip, 90b...back side of semiconductor chip 901... Semiconductor chip group holder 903... Semiconductor chip group holder with film-like adhesive 904... Semiconductor chip group holder with adhesive curing material 91... Semiconductor chip with film-type adhesive 92…Semiconductor chip with cured adhesive 7... Mask, P... Plasma

Claims

1. The process includes using a workpiece group holder comprising a support sheet, a film-like adhesive provided on one surface of the support sheet, and a plurality of workpieces held in alignment on the side of the film-like adhesive opposite to the side of the support sheet, to produce a workpiece group holder with film-like adhesive attached in which a plurality of workpieces with film-like adhesive attached provided on one surface of the support sheet are held in alignment, by irradiating the film-like adhesive exposed between the plurality of workpieces in the workpiece group holder with plasma from the side of the plurality of workpieces, dry etching the film-like adhesive and cutting the film-like adhesive along the workpieces, A method for manufacturing a workpiece coated with a film-like adhesive, wherein the film-like adhesive contains a compound (c) having at least two radical-reactive groups.

2. The method for producing a workpiece with a film-like adhesive according to claim 1, wherein the film-like adhesive further contains a photopolymerization initiator (d) having a boiling point of 300°C or higher.

3. The method for producing a workpiece with a film-like adhesive according to claim 1, wherein the film-like adhesive further contains an acrylic resin (a1) having constituent units derived from an alkyl (meth)acrylate.

4. The method for producing a workpiece with a film-like adhesive according to claim 3, wherein the number of carbon atoms in the alkyl group constituting the alkyl ester in the alkyl (meth)acrylate is 11 or less.

5. The method for manufacturing a workpiece with a film-like adhesive according to claim 3, wherein the weight-average molecular weight of the acrylic resin (a1) is 300,000 or more.

6. The process includes a step of using a workpiece group holder with a film-like adhesive obtained by the manufacturing method described in any one of claims 1 to 4, irradiating the workpiece group holder with a film-like adhesive with energy rays from the side of the support sheet to cure the film-like adhesive, thereby producing a workpiece group holder with a cured adhesive in which a plurality of workpieces with cured adhesives provided on one surface of the support sheet are aligned and held, The compound (c) is a method for manufacturing a workpiece with an adhesive cured product, which is energy ray curable.

7. A film-like adhesive containing a compound (c) having at least two radical-reactive groups, used in the manufacturing method described in any one of claims 1 to 4.

8. A film-like adhesive composite sheet comprising a support sheet and a film-like adhesive provided on one surface of the support sheet, wherein the film-like adhesive contains a compound (c) having at least two radical-reactive groups, and used in the manufacturing method described in any one of claims 1 to 4.

Images