Film-like adhesive, film-like adhesive composite sheet, and method for manufacturing workpiece with adhesive cured product

Abstract

To provide a film-like adhesive which can normally pick up workpiece with an adhesive cured product which is obtained by cutting by irradiation with a laser beam using an energy ray curable film-like adhesive and curing with an energy beam, from a support sheet.SOLUTION: A film-like adhesive 13 has energy ray curability and a gel fraction of 13% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] When manufacturing a semiconductor device, for example, a semiconductor chip with a film adhesive is manufactured, which includes a semiconductor chip and a film adhesive provided on the back surface of the semiconductor chip (the surface opposite to the circuit surface), and this is then adhered and fixed to a circuit board using the film adhesive contained therein for mounting. The film adhesive is usually thermosetting, meaning it hardens when heated, and after the semiconductor chip with the film adhesive is adhered to the circuit board, the film adhesive is thermally hardened to fix the semiconductor chip to the circuit board.

[0003] The semiconductor chip with the film-like adhesive can be produced, for example, by the following method. First, multiple parallel grooves are formed in two mutually perpendicular directions on a semiconductor wafer from its circuit surface to its back surface, and the spacing between adjacent grooves is adjusted to obtain semiconductor chips of the desired size. Next, a backgrinding tape is applied to the circuit side of the semiconductor wafer after the grooves have been formed, and the backside of the semiconductor wafer is then ground. The backside is then ground until the grooves appear, or before the grooves appear, the semiconductor wafer is divided at the groove formation locations by vibrations applied to the semiconductor wafer while the backside is being ground, thereby producing a large number of aligned semiconductor chips. These semiconductor chips are held in place by the backgrinding tape.

[0004] Next, a film-like adhesive composite sheet (e.g., a die bonding sheet) comprising a support sheet and a film-like adhesive provided on one side of the support sheet is used, and the film-like adhesive therein is attached to the back surfaces (in other words, the grinding surfaces) of the numerous semiconductor chips mentioned above. The backgrind tape is then removed from the semiconductor chips, which are now held in place by the film adhesive. Next, the exposed portions of the film adhesive between the semiconductor chips are irradiated with laser light to cut the film adhesive along the semiconductor chips, thereby obtaining a large number of semiconductor chips with film adhesive on the support sheet, each of which includes a semiconductor chip and a cut piece of film adhesive provided on the back surface of the semiconductor chip.

[0005] These semiconductor chips with the film-like adhesive are separated from the support sheet and picked up, yielding the desired semiconductor chip with the film-like adhesive. To facilitate this pick-up, the film-like adhesive may have, in addition to the above-mentioned thermosetting properties, energy ray-curing properties, such that it hardens when exposed to energy rays such as ultraviolet light. By energy ray-curing the film-like adhesive before pick-up, the peel force between the energy ray-cured product of the film-like adhesive and the support sheet is reduced to an appropriate range, regardless of the type of support sheet. Therefore, the semiconductor chip with the cured product (semiconductor chip with adhesive-cured product) can be easily picked up from the support sheet (see Patent Document 1). Such an energy ray-cured product of the film-like adhesive can still be used as a film-like adhesive. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 4664005 Summary of the Invention [Problem to be solved by the invention]

[0007] When a semiconductor chip with a cured adhesive is manufactured by the above-mentioned method using an energy ray-curable film-like adhesive, before it is separated from the support sheet and picked up, the film-like adhesive is either cut by irradiation with laser light and then cured with energy rays, or is cured into a cured adhesive by energy ray curing and then cut by irradiation with laser light. However, in such cases, even though the film-like adhesive is energy ray-cured to reduce the peeling force during pick-up, peeling at the interface between the energy ray-cured film-like adhesive and the support sheet becomes difficult, resulting in the problem that the semiconductor chip with the cured adhesive cannot be picked up. In particular, it has been found that picking up a semiconductor chip with a cured adhesive is more difficult when the film adhesive is cured with energy rays and then cut by irradiation with laser light and then picked up than when the film adhesive is cut by irradiation with laser light and then cured with energy rays and then picked up.

[0008] So far, we have explained the problems associated with manufacturing semiconductor chips with a cured adhesive from a semiconductor wafer as an example of semiconductor device manufacturing, but similar problems can also occur when manufacturing various substrate devices, not just semiconductor devices. That is, the above-mentioned problems can also occur when manufacturing a workpiece with a cured adhesive, which includes a workpiece obtained by processing a workpiece and an energy ray-cured product of a film-like adhesive (cured adhesive product) provided on the workpiece.

[0009] The present invention aims to provide a film-like adhesive that enables a workpiece with a cured adhesive, obtained by using an energy ray-curable film-like adhesive, cutting it by irradiating it with laser light and curing it with energy rays, to be properly picked up from a support sheet. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention employs the following configuration. [1] A film-like adhesive that is energy ray curable and has a gel fraction of 13% or less. [2] A test piece (t1) having a thickness of 1000 μm, which is formed by laminating a plurality of sheets of the film-like adhesive, is used, and in the temperature range from -10 ° C to 50 ° C, the shear strain generated in the test piece (t1) at a measurement frequency of 1 Hz is increased in the range of 0.01 to 10%, and the shear storage modulus G of the test piece (t1) at a shear strain of 1% at a temperature of 23 ° C is measured. 23 When the shear storage modulus G' is measured, 23 The film adhesive according to [1], wherein the compressive strength is 8 MPa or less.

[0011] [3] The film adhesive according to [1] or [2], wherein the content of the filler (d) in the film adhesive is less than 15 mass % relative to the total mass of the film adhesive. [4] The film adhesive according to any one of [1] to [3], wherein the content of the polymer component (a) relative to the total mass of the film adhesive is 28 mass % or less. [5] The film-like adhesive according to any one of [1] to [4], wherein the energy ray-cured product of the film-like adhesive has a gel fraction of 13% or less.

[0012] [6] A film adhesive composite sheet comprising a support sheet and a film adhesive provided on one side of the support sheet, wherein the film adhesive is the film adhesive described in [1]. [7] The film-like adhesive composite sheet according to [6], wherein the support sheet consists of only a substrate.

[0013] [8] Illuminance of 230mW / cm for the film-like adhesive composite sheet 2 , light intensity 190mJ / cm 2a film-like adhesive composite sheet according to [6] or [7], wherein a 25 mm wide test piece (t3) is prepared by UV-curing the film-like adhesive by irradiating it with UV rays under the conditions of [9] A method for manufacturing a workpiece with an adhesive cured product using the film-like adhesive composite sheet described in [6] or [7], the manufacturing method using a workpiece group holder in which a plurality of workpieces are aligned and held on the surface of the film-like adhesive in the film-like adhesive composite sheet opposite to the support sheet side, and irradiating the film-like adhesive exposed between the workpieces in the workpiece group holder with laser light to cut the film-like adhesive along the workpieces, thereby forming a bond between the workpieces and the cut film-like adhesive provided on the workpieces. a cutting step of producing a workpiece with a film-like adhesive, the workpiece comprising an adhesive; an energy ray curing step of, after the cutting step, curing the film-like adhesive in the workpiece with the film-like adhesive with energy rays to produce a plurality of workpieces with an adhesive-cured product on the support sheet, the workpiece comprising the workpiece and an energy ray-cured product of the film-like adhesive provided on the workpiece; and a picking up step of, after the energy ray curing step, separating the workpiece with the adhesive-cured product from the support sheet and picking it up.

[0014]

[10] A method for manufacturing a workpiece with an adhesive cured product using the film-like adhesive composite sheet described in [6] or [7], wherein the gel fraction of the energy ray cured product of the film-like adhesive in the film-like adhesive composite sheet is 13% or less, and the manufacturing method includes using a workpiece group holder in which a plurality of workpieces are aligned and held on the surface of the film-like adhesive in the film-like adhesive composite sheet opposite to the support sheet side, and curing the film-like adhesive in the workpiece group holder with energy rays to form a cured workpiece group holder in which a plurality of workpieces are aligned and held on the energy ray cured product of the film-like adhesive. a cutting step, after the energy ray curing step, of irradiating a laser beam onto an energy ray-cured product of the film-like adhesive exposed between the workpieces in the cured workpiece group holder to cut the energy ray-cured product along the workpiece, thereby producing a workpiece with an adhesive-cured product comprising the workpiece and the cut energy ray-cured product provided on the workpiece; and a pick-up step, after the cutting step, of separating the workpiece with the adhesive-cured product from the support sheet and picking it up. [Effects of the Invention]

[0015] According to the present invention, a film-like adhesive is provided which uses an energy ray-curable film-like adhesive, which is cut by irradiating it with laser light and then cured with energy rays, and which enables a workpiece with a cured adhesive to be properly picked up from a support sheet. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a cross-sectional view schematically illustrating an example of a film adhesive according to one embodiment of the present invention. [Figure 2] 1 is a cross-sectional view schematically illustrating an example of a film-like adhesive composite sheet according to one embodiment of the present invention. [Figure 3] FIG. 3 is a cross-sectional view schematically showing another example of a film-like adhesive composite sheet according to one embodiment of the present invention. [Figure 4] 1A to 1C are cross-sectional views for schematically explaining an example of a method for manufacturing a workpiece with a cured adhesive according to an embodiment of the present invention. [Figure 5] 10A to 10C are cross-sectional views for schematically explaining another example of a method for manufacturing a workpiece with a cured adhesive according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] ◇Film adhesive A film-like adhesive according to one embodiment of the present invention is energy ray-curable and has a gel fraction of 13% or less. A workpiece with an adhesive-cured product, which includes a workpiece and an energy ray-cured product of the film-like adhesive applied somewhere on the workpiece, is used in the manufacture of a substrate device, as described below. The workpiece with an adhesive-cured product can be manufactured by cutting the film-like adhesive attached to the workpiece by irradiating it with laser light on a support sheet, as described below, curing it with energy ray, and then detaching the film-like adhesive together with the workpiece from the support sheet and picking it up. In this case, since the gel fraction of the film-like adhesive that has not been energy ray-cured is 13% or less, peeling the energy ray-cured product of the film-like adhesive (the adhesive-cured product) from the support sheet is not difficult, and the workpiece with the adhesive-cured product can be successfully picked up from the support sheet.

[0018] In this specification, unless otherwise specified, the term "film-like adhesive" refers to a film-like adhesive that has not been intentionally cured by energy rays or intentionally cured by heat. Unless otherwise specified, the term "cured adhesive product" refers to a film-like adhesive product that has been cured by energy rays.

[0019] In this specification, a workpiece is something obtained by machining a workpiece. Examples of the workpiece include a wafer and a semiconductor device panel.

[0020] Examples of the wafer include semiconductor wafers made of elemental semiconductors such as silicon, germanium, and selenium, and compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; and insulating wafers made of insulators such as sapphire and glass. For example, if the workpiece is a semiconductor wafer, the workpiece artifact may be a semiconductor chip. A circuit is formed on one surface of each of these wafers, and in this specification, the surface of the wafer on which the circuit is formed is referred to as the "circuit side," and the surface of the wafer opposite the circuit side is referred to as the "back side." The wafer is divided into chips by dicing or other means. In this specification, as with the wafer, the surface of the chip on which the circuit is formed is referred to as the "circuit side," and the surface 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, pillars, etc. The protruding electrodes are preferably made of solder.

[0021] The semiconductor device panel is handled during the manufacturing process of a semiconductor device, and a specific example thereof is a panel that uses a semiconductor device in which one or more electronic components are sealed with sealing resin, and is configured by arranging multiple such semiconductor devices in a plane within an area of ​​a circular, rectangular, or other shape.

[0022] In this specification, the term "substrate device" refers to a device formed by adhesively fixing a workpiece with a cured adhesive to a circuit board using the cured adhesive. For example, if a semiconductor wafer is used as the workpiece, the substrate device may be a semiconductor device.

[0023] The film adhesive of this embodiment can be laminated with a support sheet to form a film adhesive composite sheet, which will be described later. This film adhesive composite sheet can be used in the same way as known dicing and die bonding sheets.

[0024] The film-like adhesive of this embodiment has energy ray curing properties and may or may not also have thermosetting properties, but it is preferable that it has both energy ray curing properties and thermosetting properties. In the manufacturing process of a substrate device, a workpiece with a cured adhesive can be mounted on a circuit board by adhering it to the circuit board using the cured adhesive contained therein. Furthermore, if the cured adhesive (energy ray-cured product of the film-like adhesive) has thermosetting properties, the energy ray- and thermosetting product formed by thermally curing the cured adhesive after adhesion has high impact resistance and retains sufficient adhesive properties even under harsh conditions of high temperature and high humidity.

[0025] As used herein, "energy rays" refers to electromagnetic waves or charged particle beams that have an energy quantum. Examples of energy rays include ultraviolet rays, radioactive rays, and electron beams. Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet light source. Electron beams can be irradiated using those generated by an electron beam accelerator or the like. In this specification, "energy ray curable" means a property of being cured by irradiation with energy rays, and "non-energy ray curable" means a property of not being cured even when irradiated with energy rays. In this specification, the term "thermosetting" refers to the property of being hardened by heating.

[0026] The film-like adhesive preferably has pressure-sensitive adhesive properties. A film-like adhesive having both thermosetting and pressure-sensitive adhesive properties can be applied to various adherends by lightly pressing it when not cured by heating. The film-like adhesive may also be one that can be applied to various adherends by softening it by heating.

[0027] When the cured product of the film-like adhesive is actually used, the curing conditions for curing the film-like adhesive to form a cured product are not particularly limited, as long as the degree of cure of the cured product is sufficiently high, and may be selected appropriately depending on the type of film-like adhesive. The irradiance of the energy rays when curing the film adhesive is 60 to 320 mW / cm 2 The amount of energy rays during the energy ray curing is preferably 100 to 1000 mJ / cm. 2 It is preferable that: The heating temperature during thermal curing of the adhesive cured product and the film-like adhesive is preferably 100 to 200° C. The heating time during thermal curing is preferably 0.5 to 5 hours.

[0028] <Gel fraction of film adhesive> The gel fraction of the film-like adhesive is 13% or less. In contrast, when a workpiece with a cured adhesive is manufactured using a film-like adhesive composite sheet configured with a conventional film-like adhesive having a gel fraction exceeding 13%, unlike the present embodiment, the workpiece with a cured adhesive often cannot be properly picked up from the support sheet. The reason for this is unclear, but is presumed to be as follows. That is, when a conventional film-like adhesive is irradiated with laser light to cut the film-like adhesive, modified substances originating from the film-like adhesive are generated, and these modified substances are distributed over a wide area between the film-like adhesive and the support sheet. It is presumed that these modified substances hinder the peeling of the film-like adhesive from the support sheet after cutting, and as a result, even if the film-like adhesive is cured with energy rays, the pick-up of the workpiece with the cured adhesive from the support sheet is hindered. When such a film-like adhesive composite sheet is used, it is often observed that the surface of the workpiece is contaminated with deposits that are presumed to be the modified substances when the film-like adhesive is cut. In this way, if the pickup ability of the workpiece with the adhesive cured product becomes poor when laser light is irradiated onto the film-like adhesive, a similar problem will usually occur when laser light is irradiated onto the energy ray-cured product of the film-like adhesive (cured adhesive product) to cut the cured adhesive product. In contrast, by using the film adhesive of this embodiment, these problems are resolved.

[0029] In this specification, the property of being able to normally pick up an object to be picked up by separating it from a support sheet, such as a workpiece with a cured adhesive, from the support sheet, is sometimes referred to as "pick-up ability."

[0030] In order to obtain the above-described effects of the present invention more significantly, the lower the gel fraction of the film adhesive, the more preferable, and it may be, for example, 10% or less, 7% or less, or 4% or less. On the other hand, a film adhesive with a gel fraction of 0.5% or more can be more easily achieved. In one embodiment, the gel fraction of the film-like adhesive may be, for example, any one of 0.5 to 13%, 0.5 to 10%, 0.5 to 7%, and 0.5 to 4%, although these are just examples of the gel fraction of the film-like adhesive.

[0031] When the film adhesive contains a filler (d) described below, the gel fraction of the film adhesive is the gel fraction of the components of the film adhesive other than the filler (d). The gel fraction of the film adhesive refers to the degree of gelation when the components in the film adhesive gel. Of the components in the film adhesive, the filler (d) does not contribute to gelation, so when the film adhesive contains a filler (d) described below, the gel fraction of the film adhesive is the gel fraction of the components of the film adhesive other than the filler (d).

[0032] The gel fraction of a film-like adhesive can be measured by a known method. For example, the gel fraction of a film-like adhesive can be measured with high accuracy by the method described below. That is, the film adhesive is cut into a piece of 50 mm × 100 mm, and the piece is wrapped in a nylon mesh sheet of 100 mm × 150 mm with a mesh size of 200, and fastened with a fastener such as a stapler to form a measurement sample. 11 The measurement sample was immersed in methyl ethyl ketone (100 mL) at 25°C for 24 hours, and then the insoluble portion of the slice, the nylon mesh sheet, and the fasteners were all removed. These were then dried at 90°C for 3 hours, and further left to stand for 1 hour under conditions of 23°C and a relative humidity of 50% to condition the humidity. The mass M of the measurement sample after immersion, drying, and humidity conditioning was measured. 51 (i.e., the total mass of the insoluble portion of the piece, the mass of the nylon mesh sheet, and the mass of the fastener) was measured, and the M 51 , the mass of the measurement sample M 11 The gel fraction of the film adhesive can be calculated using the mass of the nylon mesh sheet M2, the mass of the fastener M3, and the content of the filler (d) in the film adhesive M4 according to the following formula (i). M4 can be determined by baking the film adhesive. [Gel fraction of film adhesive] = (M 51 -M2-M3-M4) / (M 11 -M2-M3-M4) x 100 (i)

[0033] The gel fraction of the film-like adhesive can be adjusted by adjusting the type or amount of the components contained in the film-like adhesive. In particular, the gel fraction of the film-like adhesive can be more easily adjusted by adjusting the type or amount of the polymer component (a), energy ray-curable component (g), coupling agent (e), or crosslinking agent (f) contained in the film-like adhesive. These components will be described in detail below.

[0034] <Gel fraction of energy ray cured film adhesive> The gel fraction of the energy ray-cured film adhesive (cured adhesive product) is preferably 13% or less. The gel fraction of the uncured film adhesive, which indicates the gel fraction of such an energy ray-cured product, tends to be even lower, and the use of such a film adhesive improves the pick-up ability of the workpiece with the cured adhesive product. Furthermore, by using such a film-like adhesive, not only can the film-like adhesive attached to the workpiece be cut by irradiating it with laser light and then cured with energy rays to form a workpiece with a cured adhesive, but also the film-like adhesive attached to the workpiece be cured by energy rays to form a workpiece with a cured adhesive, which can be cut by irradiating it with laser light to form an energy ray-cured film of the adhesive, to form a workpiece with a cured adhesive, which can be cut by irradiating it with laser light to form an energy ray-cured film of the adhesive, to form an workpiece with a cured adhesive, to form an

[0035] On the other hand, a film adhesive in which the gel fraction of the energy ray-cured product is 0.5% or more can be more easily achieved. In one embodiment, the gel fraction of the energy ray-cured product of the film-like adhesive may be, for example, 0.5 to 13%, although this is just one example of the gel fraction of the energy ray-cured product of the film-like adhesive.

[0036] The gel fraction of the energy ray cured film adhesive is calculated by applying an illuminance of 230 mW / cm 2 , light intensity 190mJ / cm 2 The gel fraction is the gel fraction of the cured product obtained by irradiating the film-like adhesive with energy rays under the conditions of (a) to (c). When the energy ray-cured product of the film-like adhesive contains a filler (d) described below, the gel fraction of the energy ray-cured product of the film-like adhesive is the gel fraction of the components of the energy ray-cured product of the film-like adhesive other than the filler (d), for the same reasons as in the case of the gel fraction of the film-like adhesive described above.

[0037] The gel fraction of the energy ray-cured film adhesive can be measured by a known method. For example, the gel fraction of the energy ray-cured film adhesive can be measured with high accuracy by the method described below. That is, in the same manner as in the measurement of the gel fraction of the film-like adhesive described above, the energy ray cured product of the film-like adhesive was cut into a piece measuring 50 mm × 100 mm, and the piece was wrapped in a nylon mesh sheet measuring 100 mm × 150 mm and having a mesh size of 200, and fastened with a fastener such as a stapler pin to form a measurement sample. 21 The measurement sample was immersed in methyl ethyl ketone (100 mL) at 25°C for 24 hours, and then the insoluble portion of the slice, the nylon mesh sheet, and the fasteners were all removed. These were then dried at 90°C for 3 hours, and further left to stand for 1 hour under conditions of 23°C and a relative humidity of 50% to condition the humidity. The mass M of the measurement sample after immersion, drying, and humidity conditioning was measured. 52 (i.e., the total mass of the insoluble portion of the piece, the mass of the nylon mesh sheet, and the mass of the fastener) was measured, and the M 52 , the mass of the measurement sample M 21 Using the mass M2 of the nylon mesh sheet, the mass M3 of the fastener, and the content M4 of the filler (d) in the film-like adhesive, the gel fraction of the energy ray-cured film-like adhesive can be calculated using the following formula (ii): [Gel fraction of energy ray cured film adhesive] = (M 52 -M2-M3-M4) / (M 21 -M2-M3-M4) x 100 (ii)

[0038] The gel fraction of the energy ray-cured film adhesive can be adjusted in the same manner as in the case of the gel fraction of the film adhesive described above.

[0039] <Film adhesive G 23 '> A test piece (t1) having a thickness of 1000 μm and constructed by laminating multiple sheets of film-like adhesive was used, and the test piece (t1) was heated from -10 ° C to 50 ° C at a heating rate of 4 ° C / min. Within this temperature range, the shear strain generated in the test piece (t1) under the condition of a measurement frequency of 1 Hz was increased in the range of 0.01 to 10%, and the shear storage modulus G of the test piece (t1) at a shear strain of 1% when the temperature was 23 ° C. 23 (In this specification, "film adhesive G 23 When the shear storage modulus G 23 The G of the film-like adhesive is preferably 8 MPa or less, more preferably 3 MPa or less, and even more preferably 1 MPa or less, and may be, for example, 0.5 MPa or less. 23 When ' is equal to or less than the upper limit, the pick-up ability of the workpiece with the cured adhesive material is improved. On the other hand, the film adhesive G 23 The lower limit of G' is not particularly limited. 23 A film adhesive with a ' of 0.04 MPa or more can be achieved more easily. In one embodiment, the film adhesive G 23 The G′ may be, for example, any of 0.04 to 8 MPa, 0.04 to 3 MPa, 0.04 to 1 MPa, and 0.04 to 0.5 MPa. However, these are the G values ​​of the film adhesive. 23 ' is an example.

[0040] The number of film adhesives constituting the test piece (t1) (in other words, the number of layers) is not particularly limited and can be appropriately selected depending on the thickness of one film adhesive. The number may be, for example, 50 to 250.

[0041] Film adhesive G 23 The above G' can be adjusted by adjusting the type or amount of the components contained in the film adhesive. In particular, the above G' can be adjusted by adjusting the type or amount of the polymer component (a), energy ray curable component (g), coupling agent (e) or crosslinking agent (f) contained in the film adhesive.23 ' can be adjusted more easily.

[0042] <G of energy ray cured film adhesive 23 '> Illuminance of 230mW / cm for a laminate of multiple film adhesives 2 , light intensity 190mJ / cm 2 A test piece (t2) having a thickness of 1000 μm was prepared by irradiating the laminate (in other words, the film-like adhesive) with energy rays under the conditions of (a) to (b) and (c) above. The test piece (t2) was heated from -10°C to 50°C at a heating rate of 4°C / min, and within this temperature range, the shear strain generated in the test piece (t2) was increased in the range of 0.01 to 10% under the condition of a measurement frequency of 1 Hz, and the shear storage modulus G of the test piece (t2) at a shear strain of 1% when the temperature was 23°C was measured. 23 (In this specification, "G of the energy ray cured product of the film-like adhesive" 23 When the shear storage modulus G 23 The G of the energy ray-cured product of the film-like adhesive is preferably 70 MPa or less, more preferably 65 MPa or less, and even more preferably 60 MPa or less. 23 By making the G ′ of such a film-like adhesive equal to or less than the upper limit, 23 The adhesive strength tends to be lower, and the use of such a film-like adhesive improves the pick-up ability of the workpiece with the cured adhesive. Furthermore, the use of such a film-like adhesive improves the adhesive strength when the workpiece with the cured adhesive is bonded to a circuit board (die bonding). On the other hand, the G of the energy ray cured film adhesive 23 The lower limit of the G′ is not particularly limited. 23 Film adhesives with a ' of 5 MPa or more can be achieved more easily. In one embodiment, the film adhesive G 23The G′ may be, for example, 5 to 70 MPa, 5 to 65 MPa, or 5 to 60 MPa. However, these are the G values ​​of the energy ray-cured product of the film-like adhesive. 23 ' is an example.

[0043] The number of sheets of the energy ray-cured film adhesive constituting the test piece (t2) (in other words, the number of layers) is not particularly limited and can be appropriately selected depending on the thickness of one sheet of the energy ray-cured film adhesive. The number may be, for example, the same as the number of sheets of the film adhesive in the test piece (t1).

[0044] G of energy ray cured film adhesive 23 ' is the G of the above film adhesive 23 It can be adjusted in the same way as for '.

[0045] <Examples of film adhesives> FIG. 1 is a cross-sectional view schematically showing an example of a film-like adhesive according to this embodiment. In addition, the drawings used in the following explanation may show enlarged essential parts for the sake of convenience in order to make the features of the present invention easier to understand, and the dimensional ratios of each component may not necessarily be the same as in reality.

[0046] The film adhesive 13 shown in Figure 1 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 the first side 13a. Such a film adhesive 13 is suitable for storage, for example, in a roll form.

[0047] The film adhesive 13 has energy ray curing properties. The gel fraction of the film adhesive 13 is 13% or less.

[0048] The first release film 151 and the second release film 152 may both be of known types. The first release film 151 and the second release film 152 may be the same as each other, or may be different from each other, for example, requiring different peeling forces when peeling them from the film-like adhesive 13. Both first release film 151 and second release film 152 are preferably release films configured by forming a silicone-based release agent layer on one side of a polyethylene terephthalate film (by silicone treatment).

[0049] In the film-like adhesive 13 shown in Figure 1, 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, and the other may be, for example, the surface to be attached to the support sheet described below.

[0050] Figure 1 shows an example in which a release film is provided on both sides (first side 13a, second side 13b) of the film-like adhesive 13, but the release film may be provided on only one side of the film-like adhesive 13, i.e., only the first side 13a or only the second side 13b.

[0051] <Other configurations of film adhesive> The film adhesive may consist of one layer (single layer) or two or more layers. When the film adhesive consists of multiple layers, these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited.

[0052] In this specification, not only in the case of film-like adhesives, "multiple layers may be the same or different from one another" means "all layers may be the same, all layers may be different, or only some layers may be the same," and further, "multiple layers are different from one another" means "at least one of the constituent materials and thicknesses of each layer is different from one another."

[0053] The thickness of the film 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 adhesive is equal to or greater than the lower limit, the strength of the film adhesive is increased and the effects obtained by using the film adhesive are enhanced. When the thickness of the film adhesive is equal to or less than the upper limit, the thickness of the film adhesive and its cured product can be prevented from becoming excessive. Here, "thickness of the film adhesive" means the thickness of the entire film adhesive; for example, the thickness of a film adhesive consisting of multiple layers means the total thickness of all layers that make up the film adhesive.

[0054] In this specification, "thickness", not limited to the case of film adhesives, means, unless otherwise specified, a value expressed as the average of thicknesses measured at five randomly selected points on the object, and can be obtained using a constant pressure thickness gauge in accordance with JIS K7130.

[0055] <<Adhesive composition>> The film-like adhesive can be formed using an adhesive composition containing the constituent materials thereof. For example, the adhesive composition can be applied to a surface on which the film-like adhesive is to be formed, and then dried as necessary to form the film-like adhesive at the desired location. The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the components in the film-like adhesive.

[0056] In the film adhesive, the proportion of the total content of one or more components described below in the film adhesive relative to the total mass of the film adhesive does not exceed 100 mass %. Similarly, in the adhesive composition, the proportion of the total content of one or more components contained in the adhesive composition, which will be described later, relative to the total mass of the adhesive composition does not exceed 100 mass %.

[0057] The adhesive composition may be applied by a known method, for example, a method using various coaters such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a roll knife coater, a curtain coater, a die coater, a knife coater, a screen coater, a Mayer bar coater, or a kiss coater.

[0058] The drying conditions for the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent as described below, it is preferable to heat-dry it. The adhesive composition containing a solvent is preferably dried, for example, at 70 to 130°C for 10 seconds to 5 minutes. The components contained in the film-like adhesive and adhesive composition will be described in detail below.

[0059] The adhesive composition may be, for example, a composition containing a polymer component (a) and an energy ray-curable component (g) (sometimes abbreviated as "composition (III)" in this specification), and it is preferable that the adhesive composition further contains a photopolymerization initiator (h). The adhesive composition for forming a film-like adhesive having both energy ray curability and thermosetting properties preferably contains a polymer component (a), an energy ray curable component (g), and a thermosetting component (b), and more preferably contains a polymer component (a), an energy ray curable component (g), a photopolymerization initiator (h), a thermosetting component (b), and a curing accelerator (c).

[0060] <Polymer component (a)> The polymer component (a) is a polymer compound that imparts film-forming properties, flexibility, etc. to the film adhesive. In this specification, the polymer compound also includes products of polycondensation reactions.

[0061] The polymer component (a) contained in the composition (III) and the film-like adhesive may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0062] Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, and the like. Among these, the polymer component (a) is preferably an acrylic resin.

[0063] The acrylic resin in the polymer component (a) may be any known acrylic polymer. The weight-average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, and may be, for example, 100,000 to 1,000,000. When the weight-average molecular weight of the acrylic resin is within this range, it becomes easy to adjust the adhesive strength between the film-like adhesive and the adherend within a preferred range. On the other hand, when the weight-average molecular weight of the acrylic resin is equal to or greater than the lower limit, the shape stability (stability over time during storage) of the film-like adhesive is improved. When the weight-average molecular weight of the acrylic resin is equal to or less than the upper limit, the film-like adhesive can more easily conform to the uneven surface of the adherend, and the occurrence of voids between the adherend and the film-like adhesive is further suppressed.

[0064] In this specification, the term "weight average molecular weight" refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC), not limited to the case of polymer component (a), unless otherwise specified.

[0065] The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70°C, more preferably -45 to 50°C, and may be, for example, -35 to 30°C. When the Tg of the acrylic resin is equal to or greater than the lower limit, the adhesive strength between the film-like adhesive and the adherend is suppressed, making it easier to pick up the workpiece with the cured adhesive from the support sheet described below. When the Tg of the acrylic resin is equal to or less than the upper limit, the adhesive strength between the film-like adhesive and the workpiece is improved.

[0066] When an acrylic resin has two or more structural units, the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox equation. The Tg of the homopolymer of the monomer from which the structural units are derived can be calculated using values ​​listed in the Polymer Data Handbook, Adhesive Handbook, or Polymer Handbook.

[0067] Examples of acrylic resins include polymers of one or more (meth)acrylic acid esters; copolymers of two or more monomers selected from the above-mentioned (meth)acrylic acid esters, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.

[0068] In this specification, the term "(meth)acrylic acid" is a concept that encompasses both "acrylic acid" and "methacrylic acid." The same applies to terms similar to (meth)acrylic acid, such as a (meth)acryloyl group.

[0069] Examples of the (meth)acrylic acid ester constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, and p) (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a chain structure and has 1 to 18 carbon atoms, such as isononyl acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, and octadecyl (meth)acrylate (stearyl (meth)acrylate); (meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; (Meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate; (Meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester; (Meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester; (Meth)acrylic acid imide; glycidyl group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate; hydroxyl group-containing (meth)acrylic acid 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; Examples include substituted amino group-containing (meth)acrylic acid esters such as N-methylaminoethyl (meth)acrylate. Here, the term "substituted amino group" refers to a group having a structure in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom.

[0070] The acrylic resin may be, for example, a resin obtained by copolymerizing one or more monomers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylolacrylamide, and the like in addition to the (meth)acrylic acid ester.

[0071] The acrylic resin may be made up of one type of monomer or two or more types of monomers, and when two or more types of monomers are used, the combination and ratio thereof can be selected arbitrarily.

[0072] The acrylic resin may or may not have a functional group capable of bonding to other compounds, such as a vinyl group, a (meth)acryloyl group, an amino group, a carboxy group, an isocyanate group, etc., in addition to the above-mentioned hydroxyl group. The functional group of the acrylic resin may bond to other compounds via a crosslinking agent (f) described below, or may bond directly to other compounds without the crosslinking agent (f).

[0073] In the present invention, a thermoplastic resin other than an acrylic resin (hereinafter sometimes simply referred to as a "thermoplastic resin") may be used as the polymer component (a) either alone or in combination with an acrylic resin. The use of such a thermoplastic resin may make it easier to pick up the workpiece with the adhesive cured product from the support sheet described below, or may make it easier for the film-like adhesive to conform to the uneven surface of the adherend, thereby further suppressing the occurrence of voids between the adherend and the film-like adhesive.

[0074] Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

[0075] The thermoplastic resin contained in composition (III) and the film-like adhesive may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0076] In the film-like adhesive, the content ratio of the polymer component (a) relative to the total mass of the film-like adhesive is preferably 28 mass% or less, regardless of the type of polymer component (a), and may be, for example, any of 23 mass% or less, 18 mass% or less, and 13 mass% or less. As will be described later, when the film-like adhesive or an energy ray-cured product thereof (adhesive-cured product) is cut by irradiating it with laser light, if the content ratio is equal to or less than the upper limit, they can be cut more easily. On the other hand, the proportion is more than 0% by mass, and is preferably 8% by mass or more in that the effects obtained by using the polymer component (a) are enhanced. In one embodiment, the ratio may be, for example, any one of 8 to 28 mass %, 8 to 23 mass %, 8 to 18 mass %, and 8 to 13 mass %, although these are just examples of the ratio.

[0077] The above content regarding the proportion of the content of polymer component (a) in the film adhesive relative to the total mass of the film adhesive is synonymous with the following: in composition (III), the proportion of the content of polymer component (a) relative to the total content of all components other than the solvent is preferably 28 mass% or less, regardless of the type of polymer component (a), and may be, for example, any one of 23 mass% or less, 18 mass% or less, and 13 mass% or less; meanwhile, the proportion is preferably greater than 0 mass% and 8 mass% or more, and in one embodiment, the proportion may be any one of 8 to 28 mass%, 8 to 23 mass%, 8 to 18 mass%, and 8 to 13 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 content ratio of the components other than the solvent is the same between the resin composition and the resin film. Therefore, in this specification, not only in the case of a film-like adhesive, the content of the components other than the solvent will mainly be described as the content in the resin film obtained by removing the solvent from the resin composition.

[0078] <Energy ray curable component (g)> The energy ray-curable component (g) is an energy ray-curable non-polymer, or an energy ray-curable oligomer or polymer (polymer) that can be considered to have been synthesized from an energy ray-curable non-polymer.

[0079] The energy ray-curable non-polymer is a component that cannot be considered as a polymer of a monomer and has energy ray-curability. The energy ray-curable non-polymer includes, for example, a compound having at least one polymerizable double bond in the molecule, and an acrylate compound having a (meth)acryloyl group is preferred.

[0080] Examples of the 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, and 1,6-hexanediol di(meth)acrylate. (meth)acrylates containing a chain aliphatic skeleton such as those listed above; (meth)acrylates containing a cyclic aliphatic skeleton 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 above polyalkylene glycol (meth)acrylates; and itaconic acid oligomers.

[0081] The weight average molecular weight of the energy ray-curable component (g) is preferably 100 to 30,000, and more preferably 300 to 10,000.

[0082] The energy ray-curable component (g) contained in the composition (III) may be one type only, or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0083] In the film-like adhesive, the content of the energy ray-curable component (g) relative to the total mass of the film-like adhesive is preferably 4 mass% or more, more preferably 6 mass% or more. When this proportion is equal to or greater than the lower limit, the film-like adhesive can be more easily cured with energy ray. On the other hand, the proportion is preferably 20% by mass or less in order to prevent excessive use of the energy ray-curable component (g). In one embodiment, the ratio may be, for example, 4 to 20% by mass or 6 to 20% by mass, although these are just examples of the ratio.

[0084] <Photopolymerization initiator (h)> The composition (III) and the film-like adhesive contain the photopolymerization initiator (h), which allows the polymerization reaction of the energy ray-curable component (g) to proceed efficiently.

[0085] Examples of the photopolymerization initiator (h) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoyl Examples of the compound include acylphosphine oxide compounds such as diphenylphosphine oxide; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl 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. Examples of the photopolymerization initiator (h) include photosensitizers such as amines.

[0086] The photopolymerization initiator (h) contained in the composition (III) and the film-like adhesive may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0087] When a photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the composition (III) and the film-like adhesive is preferably 0.1 to 12 parts by mass, more preferably 0.5 to 9 parts by mass, and particularly preferably 1 to 6 parts by mass, per 100 parts by mass of the energy ray-curable component (g).

[0088] <Thermosetting component (b)> The thermosetting component (b) has thermosetting properties and is a component for thermally curing the film-like adhesive. The thermosetting component (b) contained in the composition (III) and the film-like adhesive may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0089] 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, the term "thermosetting polyimide resin" is a general term for a polyimide precursor that forms a polyimide resin by thermal curing, and a thermosetting polyimide.

[0090] [Epoxy thermosetting resin] The epoxy thermosetting resin is composed of 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 when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0091] (Epoxy resin (b1)) Examples of the epoxy resin (b1) include known epoxy resins, such as bifunctional or higher functional epoxy compounds, including polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, orthocresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, and phenylene skeleton epoxy resins.

[0092] The number average molecular weight of the epoxy resin (b1) is not particularly limited, but is preferably 300 to 30,000 from the viewpoints of the curability of the film-like adhesive and the strength and heat resistance of the cured film-like adhesive. The epoxy equivalent of the epoxy resin (b1) is preferably 100 to 1000 g / eq, and may be, for example, either 100 to 600 g / eq or 150 to 300 g / eq.

[0093] The epoxy resin (b1) contained in the composition (III) and the film-like adhesive may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0094] 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). When the film-like adhesive contains such a combination of epoxy resins (b1), the pick-up ability of the workpiece with the adhesive cured product is improved.

[0095] 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 by mass relative to the content of the bisphenol F type epoxy resin, and may be, for example, either 5 to 12 times by mass or 7 to 12 times by mass, or either 3 to 10 times by mass or 3 to 8.5 times by mass, or either 5 to 10 times by mass or 7 to 8.5 times by mass.

[0096] 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 the epoxy resin (b1) in composition (III) and the film-like adhesive is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. When this ratio is equal to or greater than 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.

[0097] (Thermal curing agent (b2)) The thermosetting agent (b2) is a curing agent for the epoxy resin (b1). Examples of the thermosetting agent (b2) include compounds having two or more functional groups per molecule that can react with epoxy groups. Examples of the functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and anhydride groups of acid groups. Phenolic hydroxyl groups, amino groups, and anhydride groups of acid groups are preferred, and phenolic hydroxyl groups or amino groups are more preferred.

[0098] Among the heat curing agents (b2), examples of phenolic curing agents having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Among the heat curing agents (b2), examples of amine-based curing agents having an amino group include dicyandiamide (DICY).

[0099] The hydroxyl group equivalent of the heat curing agent (b2) is preferably 10 to 120 g / eq, and may be, for example, either 10 to 60 g / eq or 10 to 40 g / eq.

[0100] Of the thermosetting agents (b2), for example, the number average molecular weight of 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. Of the thermosetting agents (b2), the molecular weight of the non-resin components such as biphenol and dicyandiamide is not particularly limited, but is preferably 60 to 500, for example.

[0101] The thermosetting agent (b2) contained in the composition (III) and the film-like adhesive may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0102] When a thermosetting component (b) is used, the content of the thermosetting agent (b2) in the composition (III) and the film-like adhesive is preferably 0.5 to 10 parts by mass per 100 parts by mass of the epoxy resin (b1), and may be, for example, 0.5 to 5 parts by mass or 0.5 to 3 parts by mass. When the content of the thermosetting agent (b2) is equal to or greater than the lower limit, the thermal curing of the film-like adhesive proceeds more easily. When the content of the thermosetting agent (b2) is equal to or less than 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.

[0103] When a thermosetting component (b) is used, the content of the thermosetting component (b) in the composition (III) and the film-like adhesive (e.g., the total content of the epoxy resin (b1) and the thermosetting agent (b2)) is preferably 20 to 1,000 parts by mass, more preferably 100 to 1,000 parts by mass, per 100 parts by mass of the polymer component (a). For example, it may be 100 to 800 parts by mass, 100 to 500 parts by mass, 300 to 1,000 parts by mass, 600 to 1,000 parts by mass, or 300 to 800 parts by mass. When the content of the thermosetting component (b) is within this range, it becomes easier to adjust the adhesive strength between the film-like adhesive and the support sheet described below.

[0104] <Curing accelerator (c)> The curing accelerator (c) is a component for adjusting the thermal curing rate of the film adhesive. Preferable examples of the curing accelerator (c) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles (imidazoles in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines (phosphines in which one or more hydrogen atoms are substituted with organic groups) such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; and clathrate compounds in which the imidazoles are used as guest compounds.

[0105] The curing accelerator (c) contained in the composition (III) and the film-like adhesive may be one type or two or more types, and when there are two or more types, the combination and ratio thereof can be selected arbitrarily.

[0106] When a curing accelerator (c) is used, the content of the curing accelerator (c) in the composition (III) and the film-like adhesive is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the content of the thermosetting component (b) (e.g., the total content of the epoxy resin (b1) and the thermosetting agent (b2)). When the content of the curing accelerator (c) is equal to or greater than the lower limit, the effects of using the curing accelerator (c) are more pronounced. When the content of the curing accelerator (c) is equal to or less than the upper limit, for example, the effect of suppressing migration and segregation of the highly polar curing accelerator (c) to the adhesive interface with the adherend under high temperature and high humidity conditions in the film-like adhesive is enhanced, thereby further improving the reliability of packages obtained using the film-like adhesive.

[0107] Other ingredients The adhesive composition may or may not contain other components that do not fall under any of the polymer component (a), the energy ray-curable component (g), the photopolymerization initiator (h), the thermosetting component (b), and the curing accelerator (c). Examples of the other components include a filler (d), a coupling agent (e), a crosslinking agent (f), a colorant (i), and a general-purpose additive (j). The other components contained in the composition (III) and the film-like adhesive, such as the filler (d), coupling agent (e), crosslinking agent (f), colorant (i), and general-purpose additive (j), may each be of only one type or of two or more types, and when two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0108] <Filling material (d)> By including the filler (d), the thermal expansion coefficient of the film adhesive can be easily adjusted, and by optimizing this thermal expansion coefficient for the object to which the film adhesive is attached, the reliability of the package obtained using the film adhesive can be further improved. Furthermore, by including the filler (d) in the film adhesive, it is possible to reduce the moisture absorption rate of the cured product of the film adhesive and improve heat dissipation properties.

[0109] The filler (d) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler. Preferred inorganic fillers include, for example, powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc.; beads obtained by spheronizing these inorganic fillers; surface-modified products of these inorganic fillers; single-crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler is preferably silica, alumina, or a surface-modified product thereof.

[0110] The average particle size of the filler (d) is not particularly limited, but is preferably 10 nm to 5 μm. When the average particle size of the filler (d) is in this range, the effects of using the filler (d) can be fully obtained, and the storage stability of the film-like adhesive can be further improved.

[0111] In this specification, unless otherwise specified, the term "average particle size" refers to the particle size at 50% of the integrated value in the particle size distribution curve obtained by the laser diffraction scattering method (D 50 ) value.

[0112] In the film-like adhesive, the content of the filler (d) relative 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 or its energy ray-cured product (adhesive-cured product) is cut by irradiating it with laser light, having the content in this range makes it easier to cut. On the other hand, the proportion is 0% by mass or more. In terms of ease of cutting the above-mentioned film-like adhesive or its energy ray-cured product, it is most preferable that the proportion is 0 mass %, that is, that the film-like adhesive does not contain filler (d).

[0113] <Coupling agent (e)> By including the coupling agent (e), the film adhesive has improved adhesion and adhesion to the adherend. Furthermore, by including the coupling agent (e), the cured product has improved water resistance without impairing heat resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic or organic compound.

[0114] The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group (e.g., a second functional group) possessed by the polymer component (a), the thermosetting component (b), etc., and is more preferably a silane coupling agent.

[0115] Preferred examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane (also referred to as 3-glycidoxypropyltrimethoxysilane; the same applies to other compounds hereinafter), 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, Examples of the organosiloxane include silane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, and oligomeric or polymeric organosiloxanes.

[0116] When a coupling agent (e) is used, the content of the coupling agent (e) in the composition (III) and the film-like 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, per 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b). When the content of the coupling agent (e) is equal to or greater than the lower limit, the effects of using the coupling agent (e), such as improved dispersibility of the filler (d) in the resin and improved adhesion of the film-like adhesive to the adherend, are more significantly achieved. When the content of the coupling agent (e) is equal to or less than the upper limit, outgassing is further suppressed.

[0117] <Crosslinking agent (f)> When the polymer component (a) is a polymer such as the above-mentioned acrylic resin having a functional group such as a vinyl group, (meth)acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group that can bond with other compounds, the composition (III) and the film-like adhesive may contain a crosslinking agent (f) for bonding the functional group with other compounds to form crosslinks. Crosslinking with the crosslinking agent (f) allows the initial adhesive strength and cohesive strength of the film-like adhesive to be adjusted.

[0118] Examples of the crosslinking agent (f) 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).

[0119] In composition (III) and the film-like adhesive, the content of crosslinking agent (f) is preferably 6 parts by mass or less, more preferably 3 parts by mass or less, and is 0 part by mass or more, per 100 parts by mass of the content of polymer component (a). The lower the content of crosslinking agent (f), the higher the pick-up ability of the workpiece with the cured adhesive tends to be, and it is particularly preferable that the film-like adhesive does not contain crosslinking agent (f).

[0120] <Colorant (i)> The colorant (i) is a component that can adjust the transmittance of light of various wavelengths in the film adhesive and its cured product. Examples of the colorant (i) include known colorants such as inorganic pigments, organic pigments, and organic dyes.

[0121] When colorant (i) is used, the content of colorant (i) in the film adhesive is preferably 0.01 to 10 mass% relative to the total mass of the film adhesive, regardless of the type of colorant (i). When this proportion is equal to or greater than the lower limit, the effect of using colorant (i) is more pronounced. When this proportion is equal to or less than the upper limit, excessive use of colorant (i) is suppressed.

[0122] <General-purpose additives (j)> The general-purpose additive (j) may be a known one and may be selected arbitrarily depending on the purpose, and is not particularly limited. Preferred general-purpose additives (j) include, for example, plasticizers, antistatic agents, antioxidants, gettering agents, antifoaming agents, and leveling agents.

[0123] The content of the general-purpose additive (i) in the composition (III) and the film-like adhesive is not particularly limited and can be selected appropriately depending on, for example, the type of the general-purpose additive (i).

[0124] <Solvent> Composition (III) preferably further contains a solvent, which improves the handleability of composition (III).

[0125] In this specification, unless otherwise specified, the term "solvent" is used to refer to a concept that includes not only a substance that dissolves a target component, but also a dispersion medium that disperses the target component.

[0126] 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 composition (III) may contain only one type of solvent, or two or more types. When two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0127] The solvent contained in composition (III) is preferably methyl ethyl ketone or the like, since this allows the components contained in composition (III) to be mixed more uniformly.

[0128] The content of the solvent in the composition (III) is not particularly limited, and may be appropriately selected depending on, for example, the types of components other than the solvent.

[0129] <<Example of film adhesive>> An example of a preferred film-like adhesive of the present embodiment is a film-like adhesive having energy ray curability, wherein the gel fraction of the film-like adhesive is 13% or less, the film-like adhesive contains a polymer component (a), an energy ray-curable component (g), and a photopolymerization initiator (h); In the film-like adhesive, the content of the polymer component (a) relative to the total mass of the film-like adhesive is 28 mass% or less, The film-like adhesive does not contain filler (d), or further contains filler (d), and when the film-like adhesive contains filler (d), the content of filler (d) relative to the total mass of the film-like adhesive is more than 0 mass% and less than 15 mass%.

[0130] A more preferred example of the film-like adhesive of this embodiment is a film-like adhesive having energy ray curability, wherein the gel fraction of the film-like adhesive is 13% or less, the film-like adhesive comprises a polymer component (a), an energy ray-curable component (g), a photopolymerization initiator (h), a thermosetting component (b), and a curing accelerator (c); In the film-like adhesive, the content of the polymer component (a) relative to the total mass of the film-like adhesive is 28 mass% or less, In the film-like adhesive, the content of the energy ray-curable component (g) relative to the total mass of the film-like adhesive is 4 mass% or more, In the film-like adhesive, the content of the thermosetting component (b) is 100 to 1000 parts by mass per 100 parts by mass of the content of the polymer component (a), The film-like adhesive does not contain filler (d), or further contains filler (d), and when the film-like adhesive contains filler (d), the content of filler (d) relative to the total mass of the film-like adhesive is more than 0 mass% and less than 15 mass%.

[0131] <<Method of manufacturing adhesive composition>> The adhesive composition (for example, composition (III)) can be obtained by blending the components that constitute it. The order of addition of the components when blending is not particularly limited, and two or more components may be added simultaneously. When a solvent is used, the solvent may be mixed with any of the ingredients other than the solvent to pre-dilute the ingredients, or the solvent may be mixed with any of the ingredients other than the solvent without pre-diluting these ingredients.

[0132] The method for mixing the components during blending is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or stirring blades, a method of mixing using a mixer, or a method of mixing by adding ultrasound. The temperature and time for adding and mixing each component are not particularly limited as long as the components do not deteriorate, and may be adjusted appropriately. A temperature of 15 to 30°C is preferred.

[0133] ◇Film 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 side of the support sheet, and the film-like adhesive is the film-like adhesive according to one embodiment of the present invention described above. The film-like adhesive composite sheet of this embodiment can be used, for example, as a sheet for cutting a film-like adhesive or its energy ray-cured product attached to a workpiece by irradiating it with laser light. In either case, as will be described later, the workpiece with the cured adhesive obtained after irradiating it with laser light is finally separated from the support sheet and picked up. In the film-like adhesive composite sheet of this embodiment, since the gel fraction of the film-like adhesive is 13% or less, the workpiece with the cured adhesive can be easily peeled off from the support sheet and can be picked up normally from the support sheet.

[0134] <<Support sheet>> The support sheet may consist of one layer (single layer) or two or more layers. When the support sheet consists of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different, and the combination of these multiple layers is not particularly limited as long as it does not impair the effects of the present invention.

[0135] Examples of the support sheet include those consisting of only a substrate; those comprising a substrate and an adhesive layer provided on one side of the substrate; and those constructed by laminating a substrate, an adhesive layer, and an intermediate release layer in this order in the thickness direction.

[0136] When the support sheet comprises the substrate and the adhesive layer, the adhesive layer is disposed between the substrate and the film adhesive in the film adhesive composite sheet. When the support sheet comprises the substrate, adhesive layer, and intermediate release layer, the adhesive layer and intermediate release layer are disposed between the substrate and the film adhesive in the film adhesive composite sheet. The adhesive layer and intermediate release layer are layers that make it easier to pick up the workpiece with the cured adhesive, which will be described later, from the support sheet.

[0137] The film-like adhesive composite sheet is used by attaching the surface of the film-like adhesive opposite to the support sheet side (for example, the first surface) to the workpiece or workpiece product. For example, if the workpiece is a semiconductor wafer, the film-like adhesive composite sheet is used by attaching the film-like adhesive therein to the backside of the semiconductor wafer or semiconductor chip.

[0138] When a support sheet consisting of only a substrate is used, a film-like adhesive composite sheet can be produced at low cost. When a support sheet comprising a substrate and a pressure-sensitive adhesive layer is used, the adhesive strength between the support sheet (more specifically, the pressure-sensitive adhesive layer) and the film-like adhesive in the film-like adhesive composite sheet can be easily adjusted. Furthermore, when a support sheet consisting of only a substrate is used, a jig adhesive layer must be provided separately on the substrate when fixing the film-like adhesive composite sheet to a fixing jig such as a ring frame. However, when a support sheet comprising a substrate and a pressure-sensitive adhesive layer is used, the film-like adhesive composite sheet can be fixed to the fixing jig by the pressure-sensitive adhesive layer, so the jig adhesive layer can be omitted. Even when a support sheet having a substrate, a pressure-sensitive adhesive layer, and an intermediate release layer is used, the adhesive strength between the support sheet (more specifically, the intermediate release layer) and the film-like adhesive in the film-like adhesive composite sheet can be easily adjusted. In this case, too, the pressure-sensitive adhesive layer can be used to fix the film-like adhesive composite sheet to the fixing jig, so the jig adhesive layer can be omitted.

[0139] The film-like adhesive composite sheet may further comprise a release film on the surface of the film-like adhesive opposite to the support sheet side (for example, the first surface).

[0140] The configuration of the film-like adhesive composite sheet of this embodiment will be described below for each type of support sheet.

[0141] FIG. 2 is a cross-sectional view schematically showing an example of the film-like adhesive composite sheet of this embodiment. In FIG. 2 and subsequent figures, the same components as those shown in the figures already described are given the same reference numerals as in the figures already described, and detailed description thereof will be omitted.

[0142] The film-like adhesive composite sheet 101 shown in Figure 2 is composed of a support sheet 10 and a film-like adhesive 13 provided on one surface 10a of the support sheet 10 (sometimes referred to as the "first surface" in this specification). The film adhesive 13 is the film adhesive 13 shown in FIG.

[0143] The support sheet 10 is made of only a 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.

[0144] In the film-like adhesive composite sheet 101, a jig adhesive layer 16 is provided in the area near the periphery of the film-like adhesive 13 (the area with a circular planar shape along the periphery) on the surface (first surface) 13a of the film-like adhesive 13 opposite the support sheet 10 side.

[0145] The film-like adhesive composite sheet 101 further comprises a release film 15 in an 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 an area near the peripheral edge of the film-like adhesive 13. In the film-like adhesive composite sheet 101, the release film 15 is an optional configuration.

[0146] When the film-like adhesive composite sheet 101 is used, the release film 15 is removed and a workpiece or workpiece compound is attached to the first surface 13a of the film-like adhesive 13. The surface of the jig adhesive layer 16 opposite the film-like adhesive 13 is attached to a fixing jig.

[0147] FIG. 3 is a cross-sectional view schematically showing another example of the film-like adhesive composite sheet of the present embodiment. The film-like adhesive composite sheet 102 shown in Figure 3 is composed of a support sheet 20 and a film-like adhesive 13 provided on one surface 20a of the support sheet 20 (sometimes referred to as the "first surface" in this specification).

[0148] The support sheet 20 is constructed by laminating a substrate 11, a pressure-sensitive adhesive layer 12, and an intermediate release layer 14 in this order in the thickness direction. One surface (first surface) 20a of the support sheet 20 is the same as one surface 14a of the intermediate release layer 14. The other surface 20b of the support sheet 20 (the surface opposite to the film-like adhesive 13 side) is the same as the other surface 11b of the substrate 11.

[0149] In the film-like adhesive composite sheet 102, of the surface 12a of the adhesive layer 12 opposite the substrate 11 side (sometimes referred to as the "first surface" in this specification), the area near the peripheral edge of the adhesive layer 12 (the area along the peripheral edge) is exposed, and in the other areas, an intermediate release layer 14 and a film-like adhesive 13 are laminated in this order in the direction away from the adhesive layer 12 (the same direction as the direction from the substrate 11 side to the adhesive layer 12 side).

[0150] The film-like adhesive composite sheet 102 further comprises a release film 15 on the area of ​​the first surface 12a of the pressure-sensitive adhesive layer 12 where the intermediate release layer 14 and the film-like adhesive 13 are not provided, and on the first surface 13a of the film-like adhesive 13. In the film-like adhesive composite sheet 102, the release film 15 is an optional component.

[0151] The film-like adhesive composite sheet 102 is used with the release film 15 removed, and a workpiece or a processed workpiece is attached to the first surface 13a of the film-like adhesive 13. Of the first surface 12a of the pressure-sensitive adhesive layer 12, the exposed area near the periphery of the pressure-sensitive adhesive layer 12 (the exposed area along the periphery) is attached to a fixing jig.

[0152] The film-like adhesive composite sheet of this embodiment is not limited to that shown in Figures 2 and 3, and for example, some of the configurations of these film-like adhesive composite sheets may be changed, deleted, or added within the scope of the present invention.

[0153] Next, each layer constituting the film-like adhesive composite sheet of this embodiment will be described in more detail.

[0154] <Base material> The substrate may be in the form of a sheet or film, and may be any known substrate. Examples of materials that can be used for the substrate include various resins. Examples of the resin include polyolefins such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and polypropylene; ethylene-based copolymers (copolymers obtained using ethylene as a monomer) such as ethylene-vinyl acetate copolymer and ethylene-(meth)acrylic acid copolymer; vinyl chloride-based resins (resins obtained using vinyl chloride as a monomer); polyester; and polyimide. Examples of the resin include crosslinked resins in which one or more of the resins exemplified above are crosslinked; and modified resins such as ionomers using one or more of the resins exemplified above.

[0155] The resin constituting the substrate may be one type only, or two or more types, and when two or more types are used, the combination and ratio thereof can be selected arbitrarily.

[0156] The substrate may consist of one layer (single layer), or may consist of two or more layers. When the substrate consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

[0157] The thickness of the substrate is preferably 50 to 300 μm, more preferably 60 to 140 μm. By keeping the thickness of the substrate within this range, the flexibility of the film-like adhesive composite sheet and its suitability for application to a workpiece are further improved. Here, the "thickness of the substrate" means the thickness of the entire substrate, and for example, the thickness of a substrate consisting of multiple layers means the total thickness of all layers that make up the substrate.

[0158] The substrate may contain, in addition to the main constituent materials such as the resin, various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

[0159] The substrate may be either transparent or non-transparent, may be colored depending on the purpose, or may have other layers vapor-deposited thereon. The substrate is preferably one that transmits energy rays.

[0160] In order to adjust the adhesion to a layer (for example, a film adhesive, a pressure-sensitive adhesive layer, or the other layer) provided thereon, the substrate may or may not be subjected to a surface roughening treatment such as sandblasting or solvent treatment; an oxidation treatment such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, flame treatment, chromic acid treatment, or hot air treatment; an oleophilic treatment; a hydrophilic treatment; etc. Furthermore, the substrate surface may or may not be treated with a primer.

[0161] The substrate may contain a specific range of components (for example, a resin) to provide adhesiveness on at least one surface.

[0162] The substrate can be produced by a known method. For example, a substrate containing a resin can be produced by molding a resin composition containing the resin.

[0163] <Adhesive layer> The pressure-sensitive adhesive layer is in the form of a sheet or film and contains a pressure-sensitive adhesive. The adhesive layer may be a known adhesive layer. Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber-based resins, silicone resins, epoxy-based resins, polyvinyl ethers, polycarbonates, and ester-based resins.

[0164] The adhesive layer may consist of one layer (single layer), or may consist of two or more layers. When it consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

[0165] The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm, and may be, for example, either 1 to 60 μm or 1 to 30 μm. Here, "thickness of the adhesive layer" means the thickness of the entire adhesive layer, and for example, the thickness of an adhesive layer consisting of multiple layers means the total thickness of all layers that make up the adhesive layer.

[0166] The pressure-sensitive adhesive layer may be either transparent or non-transparent, and may be colored depending on the purpose. The pressure-sensitive adhesive layer is preferably one that transmits energy rays.

[0167] The pressure-sensitive adhesive layer may be either energy ray-curable or non-energy ray-curable. The physical properties of the energy ray-curable pressure-sensitive adhesive layer can be adjusted before and after curing. For example, by curing the energy ray-curable pressure-sensitive adhesive layer before picking up the workpiece with the cured adhesive, as described below, the workpiece with the cured adhesive can be more easily picked up from the support sheet.

[0168] The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive. For example, the pressure-sensitive adhesive composition can be applied to a surface on which the pressure-sensitive adhesive layer is to be formed, and then dried as necessary to form the pressure-sensitive adhesive layer at the desired location. The ratio of the contents of the components that do not vaporize at room temperature in the pressure-sensitive adhesive composition is usually the same as the ratio of the contents of the components in the pressure-sensitive adhesive layer.

[0169] The application and drying of the pressure-sensitive adhesive composition can be carried out, for example, by the same method as in the application and drying of the adhesive composition described above.

[0170] When the adhesive layer is energy ray curable, examples of the energy ray curable adhesive composition include an adhesive composition (I-1) containing a non-energy ray curable adhesive resin (I-1a) 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 has been introduced into the side chain of the non-energy ray curable adhesive resin (I-1a); and an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray curable compound.

[0171] When the pressure-sensitive adhesive layer is non-energy ray curable, examples of the non-energy ray curable pressure-sensitive adhesive composition include a pressure-sensitive adhesive composition (I-4) containing the non-energy ray curable pressure-sensitive adhesive resin (I-1a).

[0172] <Intermediate release layer> The intermediate release layer may be in the form of a sheet or film, and may be any known material.

[0173] Examples of intermediate release layers include an intermediate release layer consisting of a single resin layer, and an intermediate release layer consisting of multiple layers including a resin main body (resin layer) and a release treatment layer provided on one side of the main body. The intermediate release layer having the release treatment layer is arranged in the film-like adhesive composite sheet with the release treatment layer facing the film-like adhesive side.

[0174] Among the intermediate release layers provided with a release treatment layer, the resin layer can be produced by molding a resin composition containing a resin. An intermediate release layer consisting of a single resin layer can also be produced in the same manner. The intermediate release layer having a release-treated layer can be produced by subjecting one surface of the resin layer to a release treatment.

[0175] The release treatment of one surface of the resin layer can be carried out using various known release agents, such as alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, or wax-based release agents.

[0176] In an intermediate release layer having a release treatment layer, examples of the resin that is the constituent material of the resin layer include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), etc. Examples of the resin constituting the intermediate release layer consisting of a single resin layer include ethylene-vinyl acetate copolymer, etc. In the ethylene-vinyl acetate copolymer, the proportion of the amount of structural units derived from vinyl acetate relative to the total amount of structural units is preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0177] In an intermediate release layer having a release treatment layer, the resin layer that forms the main body may consist of one layer (single layer) or may consist of two or more layers.If it consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

[0178] In the case of an intermediate release layer that is made up of a plurality of resin layers, it is sufficient that the surface of the outermost layer (outermost surface) on the side that has the film-like adhesive is subjected to release treatment.

[0179] The thickness of the intermediate release layer is preferably 10 to 200 μm. When the thickness of the intermediate release layer is equal to or greater than the lower limit, the intermediate release layer becomes easier to handle and is more effectively prevented from being broken or otherwise damaged. On the other hand, when the thickness of the intermediate release layer is equal to or less than the upper limit, the force exerted from the support sheet side when picking up the workpiece with the cured adhesive is more easily transmitted to the workpiece with the cured adhesive, making picking up easier. Here, the "thickness of the intermediate release layer" means the thickness of the entire intermediate release layer, that is, the total thickness of all layers that make up the intermediate release layer.

[0180] <Release film> The release film is the same as the first release film or the second release film (first release film 151 or second release film 152 shown in FIG. 1) described above.

[0181] <Adhesive layer for jig> The jig adhesive layer may be a known adhesive layer. The adhesive layer for the jig may be, for example, a single-layer structure containing an adhesive component, or a multi-layer structure in which layers containing adhesive components are laminated on both sides of a core sheet.

[0182] <Other layers> The film-like adhesive composite sheet of this embodiment may or may not have other layers at any location that do not fall under any of the following: a substrate, a pressure-sensitive adhesive layer, an intermediate release layer, a film-like adhesive, a release film, and a jig adhesive layer. The other layers can be arbitrarily selected depending on the purpose and are not particularly limited.

[0183] The other layer may consist of one layer (single layer) or two or more layers. When it consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited.

[0184] The thickness of the other layer can be selected arbitrarily depending on the type of the other layer, and is not particularly limited.

[0185] The film-like adhesive composite sheet of this embodiment preferably 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 pick-up ability of the workpiece with the cured adhesive attached thereto is improved.

[0186] <<Peel strength between the energy ray cured film adhesive and the support sheet>> The use of the film-like adhesive composite sheet of this embodiment improves the pick-up ability of the workpiece with the adhesive cured product, because the use of the film-like adhesive reduces the peel force between the energy ray cured product and the support sheet within an appropriate range. That is, the degree of pick-up ability of a workpiece with a cured adhesive can be determined using the peel force between the energy ray-cured product of the film-like adhesive (cured adhesive product) and the support sheet as an index.

[0187] The film-like adhesive composite sheet of this embodiment is irradiated with an illuminance of 230 mW / cm from the support sheet side. 2 , light intensity 190mJ / cm 2 A 25 mm wide test piece (t3) was prepared by irradiating the film-like adhesive with energy rays under the conditions of (a) to (c), and (b) the support sheet was peeled from the energy ray-cured product of the film-like adhesive of the test piece (t3). A peel test (so-called 180° peel) was performed in which the support sheet was peeled from the energy ray-cured product of the film-like adhesive in the length direction at a peel rate of 300 mm / min, with the angle between the surface of the energy ray-cured product of the energy ray-cured product and the surface of the support sheet to which the energy ray-cured product of the energy ray-cured product was attached being 180°. The peel force between the energy ray-cured product of the film-like adhesive and the support sheet was preferably 100 mN / 25 mm or less. Use of such a film-like adhesive composite sheet improves the pick-up ability of workpieces with cured adhesive attached.

[0188] More specifically, the peel test can be carried out, for example, by the following method. That is, first, a rectangular piece having a width of 25 mm and a length of preferably 200 mm or more is cut out from the film-like adhesive composite sheet. Then, this piece is irradiated with an illuminance of 230 mW / cm from the support sheet side. 2 , light intensity 190mJ / cm 2 The film-like adhesive in the slice is cured by energy rays (e.g., ultraviolet rays) under the conditions of

[0043] , thereby producing a test piece (t3). The film-like adhesive composite sheet may have a release film as shown in Figures 2 and 3, and the test piece (t3) may have or may not have a release film.

[0189] Next, the support sheet is peeled off from the energy ray-cured product of the film-like adhesive in the test piece (t3). At this time, it is preferable to attach the cured product to a rigid support using an attachment means such as double-sided tape to fix the test piece (t3) to the rigid support, and then use this fixed test piece (t3) to measure the peel force. Fixing the test piece (t3) in this manner allows the peel force to be measured with higher accuracy. The rigid support can be one that does not deform during the measurement of the peel force, and is preferably a plate-shaped or block-shaped support made of resin or metal. The test piece (t3) is preferably fixed to the hard support in an environment of a temperature of 23°C and a relative humidity (RH) of 50%. When fixing the test piece (t3) to the hard support, it is preferable to press the laminate of the hard support, the attachment means, and the test piece (t3) by, for example, pressing a rubber roller against the laminate and moving it back and forth. After being fixed to the hard support, the test piece (t3) is preferably left to stand for 30 minutes or more in an environment of 23°C and 50% relative humidity (RH) before measuring the peel force to stabilize the fixed state. By performing any one or all of these steps and sufficiently fixing the test piece (t3) to the hard support, the peel force can be measured with higher accuracy.

[0190] In the test piece (t3), the support sheet is peeled off from the energy ray-cured film adhesive, with the cured product fixed in place, so that the surfaces that were in contact with each other form an angle of 180°. The peeling speed is 300 mm / min. The measured peel strength value obtained at this time is used as the peel strength between the energy ray-cured film adhesive and the support sheet.

[0191] The peel strength between the energy ray-cured film adhesive and the support sheet is preferably 90 mN / 25 mm or less. On the other hand, in order to be highly effective in preventing the workpiece with the cured adhesive from being unintentionally peeled off from the support sheet, the peel force is preferably 10 mN / 25 mm or more. In one embodiment, the peeling force may be, for example, any one of 10 to 100 mN / 25 mm and 10 to 90 mN / 25 mm, although these are just examples of the peeling force.

[0192] The peel strength between the energy ray-cured product of the film-like adhesive and the support sheet can be adjusted, for example, by adjusting the types or amounts of the components contained in the film-like adhesive. In particular, the peel strength can be more easily adjusted by adjusting the types or amounts of the polymer component (a), energy ray-curable component (g), coupling agent (e), or crosslinking agent (f) contained in the film-like adhesive.

[0193] ◇Manufacturing method for film-type adhesive composite sheet The film-like adhesive composite sheet of this embodiment can be produced by laminating the above-mentioned layers in a corresponding positional relationship and adjusting the shape of some or all of the layers as necessary. The method for forming each layer is as described above.

[0194] For example, when a film-like adhesive is laminated on a support sheet, the adhesive composition described above may be applied to the support sheet and then dried as necessary. Alternatively, the film adhesive can be laminated on the support sheet by applying the adhesive composition to a release film and drying it as necessary to form a film adhesive on the release film, and then laminating the exposed surface of this film 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.

[0195] So far, the case of laminating a film-like adhesive on a substrate has been described as an example, but the above-mentioned method can also be applied to the case of laminating a pressure-sensitive adhesive layer on a substrate when producing a support sheet, for example. When laminating a pressure-sensitive adhesive layer, the above-mentioned pressure-sensitive adhesive composition is used.

[0196] For example, when laminating a new layer (hereinafter abbreviated as "second layer") on a top layer (hereinafter abbreviated as "first layer") already laminated on a substrate, the second layer can be formed in advance on a release film using a composition for forming the second layer, and the exposed surface of the formed second layer opposite 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 laminate structure (in other words, a laminate structure of the first and second layers). In this case, the composition is preferably applied to the release-treated surface of the release film. When the second layer is the film-like adhesive, the adhesive composition is used as the composition for forming the second layer. The release film can be removed as needed after the formation of the laminate structure. Alternatively, one of the release films may be left untouched after the formation of the laminate structure and used as the outermost release film in the film-like adhesive composite sheet (e.g., release film 15 shown in Figures 2 to 4).

[0197] When laminating an intermediate release layer on a substrate, a previously prepared intermediate release layer may be laminated to the desired lamination location (for example, a pressure-sensitive adhesive layer).

[0198] ◇Method for manufacturing workpieces with cured adhesive (method for using film-type adhesive composite sheets) The film-like adhesive composite sheet can be used to manufacture a workpiece with a cured adhesive, and the obtained workpiece with a cured adhesive can further be used to manufacture a substrate device. By using the film-like adhesive composite sheet, when manufacturing a workpiece with a cured adhesive, the film-like adhesive is cut by irradiating it with laser light, and then when it is cured with energy rays, the workpiece with the cured adhesive can be properly picked up from the support sheet. Furthermore, by selecting a film-like adhesive whose energy ray-cured product has a gel fraction of 13% or less, even if the film-like adhesive is cured into an adhesive cured product by energy ray curing and then cut by irradiating it with laser light, the workpiece with the cured adhesive can be properly picked up from the support sheet, thereby expanding the options for manufacturing semiconductor chips with cured adhesive.

[0199] <<Manufacturing method (1)>> A method for manufacturing a workpiece with a cured adhesive material according to one embodiment of the present invention is a method for manufacturing a workpiece with a cured adhesive material using the film-like adhesive composite sheet according to one embodiment of the present invention described above, The manufacturing method includes a cutting step of using a workpiece group holder in which a plurality of workpieces are aligned and held on the surface of the film-like adhesive in the film-like adhesive composite sheet opposite to the support sheet side, and irradiating the film-like adhesive exposed between the workpieces in the workpiece group holder with laser light to cut the film-like adhesive along the workpieces, thereby producing a workpiece with film-like adhesive, which includes the workpieces and the cut film-like adhesive provided on the workpieces; an energy ray curing step of, after the cutting step, curing the film-like adhesive in the workpiece with the film-like adhesive with energy rays, thereby producing a plurality of workpieces with adhesive-cured material on the support sheet, each workpiece comprising the workpiece and an energy ray-cured product of the film-like adhesive provided on the workpiece; After the energy ray curing step, a pick-up step is performed to separate the workpiece with the adhesive cured product from the support sheet and pick it up (in this specification, this manufacturing method may be referred to as "manufacturing method (1)").

[0200] This manufacturing method (manufacturing method (1)) is characterized by using the film-like adhesive composite sheet, cutting the film-like adhesive therein by irradiating it with laser light, and curing the film-like adhesive after cutting with energy rays, thereby producing a workpiece with a cured adhesive. According to manufacturing method (1), unlike conventional manufacturing methods, an energy ray-curable film adhesive is used, and the workpiece with the cured adhesive obtained by cutting it by irradiating it with laser light and curing it with energy rays can be properly picked up from the support sheet.

[0201] <Method for manufacturing a semiconductor chip with a cured adhesive (Manufacturing method (1-1))> The manufacturing method (1) when the workpiece is a semiconductor wafer is a manufacturing method of a semiconductor chip with a cured adhesive using the film-like adhesive composite sheet, The manufacturing method (1) includes a cutting step (sometimes referred to in this specification as "cutting step (1-1)") of using a semiconductor chip group holder in which a plurality of semiconductor chips are aligned on the surface of the film adhesive in the film adhesive composite sheet opposite to the support sheet side and are held by the backside of the semiconductor chips, and irradiating the film adhesive exposed between the semiconductor chips in the semiconductor chip group holder with laser light to cut the film adhesive along the semiconductor chips, thereby producing a semiconductor chip with a film adhesive that includes the semiconductor chips and the cut film adhesive provided on the backside of the semiconductor chips; After the cutting step, an energy ray curing step (sometimes referred to in this specification as "energy ray curing step (1-1)") is performed to produce a plurality of semiconductor chips with adhesive-cured material on the support sheet by energy ray curing the film-like adhesive in the semiconductor chip with film-like adhesive, the semiconductor chips each comprising an energy ray-cured product of the film-like adhesive provided on the back surface of the semiconductor chip; After the energy ray curing step, there is a pick-up step (sometimes referred to in this specification as "pick-up step (1-1)") of detaching the semiconductor chip with the adhesive cured product from the support sheet and picking it up (this manufacturing method may be referred to in this specification as "manufacturing method (1-1)").

[0202] The manufacturing method (1-1) will be described below with reference to the drawings. 4 is a cross-sectional view for schematically explaining an example of the manufacturing method (1-1). Here, the manufacturing method (1-1) will be explained in the case where the film-like adhesive composite sheet 101 shown in FIG. 2 is used.

[0203] [Cutting process (1-1)] In the cutting step (1-1) of the manufacturing method (1-1), first, a semiconductor chip group holder 901 as shown in FIG. 4(a) is prepared. The semiconductor chip group holder 901 is configured by holding a plurality of semiconductor chips 90 in an aligned state on the first surface 13a of the film adhesive 13 in the film adhesive composite sheet 101. All of the semiconductor chips 90 have their back surfaces 90b held by the first surface 13a of the film adhesive 13.

[0204] The semiconductor chip group holder 901 can be produced by a known method. For example, in a semiconductor wafer before it is divided into semiconductor chips 90, multiple parallel grooves are formed in two mutually perpendicular directions from the circuit surface to the back surface (so-called half cuts are performed). At this time, the spacing between adjacent grooves is adjusted so as to obtain semiconductor chips 90 of the desired size. The circuit surface and back surface of the semiconductor wafer will become the circuit surface 90a and back surface 90b of the semiconductor chips 90, respectively, when the semiconductor wafer is subsequently divided. Next, a backgrind tape is applied to the circuit surface of the semiconductor wafer after the grooves have been formed, and the back surface of the semiconductor wafer is then ground. The back surface is then ground until the grooves appear, or before the grooves appear, the semiconductor wafer is divided at the groove formation portions by vibrations applied to the semiconductor wafer while the back surface is being ground. In this manner, a plurality of aligned semiconductor chips 90 are fabricated, which are held by the backgrind tape.

[0205] Next, one film-like adhesive composite sheet 101 is used, and the first surface 13a of the film-like adhesive 13 therein is affixed to the back surfaces 90b (in other words, the ground surfaces) of the plurality of semiconductor chips 90 described above all at once. The backgrind tape is then removed from these semiconductor chips 90. As a result of the above, a semiconductor chip group holder 901 shown in FIG. 4(a) is obtained.

[0206] In the cutting step (1-1) of the manufacturing method (1-1), as shown in FIG. 4(b), laser light R is irradiated onto the film-like adhesive 13 exposed between the semiconductor chips 90 in the semiconductor chip group holder 901, and the film-like adhesive 13 is cut along the semiconductor chips 90. 4(c), a plurality of semiconductor chips 91 with a film-like adhesive are produced, each of which includes a semiconductor chip 90 and a cut piece of film-like adhesive 130 provided on the back surface 90b of the semiconductor chip 90. These plurality of semiconductor chips 91 with a film-like adhesive are aligned and held on the support sheet 10 (in other words, the base material 11), and together with the support sheet 10, form a group 902 of semiconductor chips with a film-like adhesive. The first surface 130a and the second surface 130b of the cut film-like adhesive 130 originate from the first surface 13a and the second surface 13b of the film-like adhesive 13 before cutting, respectively.

[0207] In this specification, the "cut film adhesive" may be simply referred to as the "film adhesive", regardless of the case of production method (1-1).

[0208] The wavelength of the laser light R used to cut the film adhesive 13 is preferably 300 to 400 nm, and the output of the laser light R is preferably 0.01 to 1 W.

[0209] By using the film-like adhesive 13, typically, no contaminants originating from the film-like adhesive 13 are found on the surfaces (first surfaces 90a, side surfaces, etc.) of the semiconductor chips 90 in the group 902 of semiconductor chips with film-like adhesive obtained by the cutting process (1-1), thereby suppressing contamination of the semiconductor chips 90.

[0210] [Energy ray curing process (1-1)] After the cutting step (1-1) of the manufacturing method (1-1), in the energy ray curing step (1-1), the film-like adhesive 130 in the semiconductor chip 91 with the film-like adhesive is cured with energy rays, thereby producing a plurality of semiconductor chips 92 with an adhesive-cured product on the support sheet 10, each of which includes a semiconductor chip 90 and an energy ray-cured product 131 of the film-like adhesive provided on the back surface 90b of the semiconductor chip 90, as shown in Fig. 4(d). These plurality of semiconductor chips 92 with the adhesive-cured product are aligned and held on the support sheet 10, and together with the support sheet 10, constitute a group 903 of semiconductor chips with an adhesive-cured product. The first surface 131a and the second surface 131b of the energy ray-cured film adhesive 131 originate from the first surface 130a and the second surface 130b of the cut film adhesive 130, respectively.

[0211] The energy ray irradiation conditions (illuminance, amount of light) when the film adhesive 130 is cured with energy ray are as described above.

[0212] [Pickup process (1-1)] After the energy ray curing step (1-1) of the manufacturing method (1-1), in the pick-up step (1-1), the semiconductor chip 92 with the cured adhesive is separated from the support sheet 10 and picked up, as shown in FIG. 4(e). This allows the desired semiconductor chip 92 with the cured adhesive to be taken out.

[0213] In the pick-up step (1-1), peeling occurs between the second surface 131b of the energy ray-cured product 131 of the film-like adhesive in the semiconductor chip 92 with the adhesive-cured product and the first surface 10a of the support sheet 10. In the pick-up process (1-1), by using the film-like adhesive 13, it is not difficult to peel off the energy ray-cured product (cured adhesive product) 131 of the film-like adhesive from the support sheet 10, and the semiconductor chip 92 with the cured adhesive product can be picked up normally from the support sheet 10.

[0214] The semiconductor chip 92 with the cured adhesive attached can be picked up by a known method. For example, the semiconductor chip 92 with the cured adhesive 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 separating means 7 such as a vacuum collet to separate the semiconductor chip 92 with the cured adhesive in the direction of arrow P.

[0215] <<Manufacturing method (2)>> A method for manufacturing a workpiece with a cured adhesive material according to one embodiment of the present invention is a method for manufacturing a workpiece with a cured adhesive material using the film-like adhesive composite sheet according to one embodiment of the present invention described above, the gel fraction of the energy ray-cured product of the film-like adhesive in the film-like adhesive composite sheet is 13% or less; The manufacturing method includes an energy ray curing step of using a workpiece group holder in which a plurality of workpieces are aligned and held on a surface of the film-like adhesive in the film-like adhesive composite sheet opposite to the support sheet side, and curing the film-like adhesive in the workpiece group holder with energy rays to produce a hardened workpiece group holder in which a plurality of workpieces are aligned and held on the energy ray-hardened product of the film-like adhesive; a cutting step of, after the energy ray curing step, irradiating a laser beam onto the energy ray-cured material of the film-like adhesive exposed between the workpieces in the cured workpiece group holder to cut the energy ray-cured material along the workpieces, thereby producing a workpiece with an adhesive-cured material, which includes the workpieces and the cut energy ray-cured material provided on the workpieces; After the cutting step, a pick-up step is performed to separate the workpiece with the adhesive cured product from the support sheet and pick it up (in this specification, this manufacturing method may be referred to as "manufacturing method (2)").

[0216] This manufacturing method (manufacturing method (2)) is characterized in that a workpiece with a cured adhesive is produced using the film-like adhesive composite sheet, by curing the film-like adhesive therein with energy rays, and then cutting the energy ray-cured film-like adhesive thus formed by irradiating it with laser light. According to manufacturing method (2), unlike conventional manufacturing methods, an energy ray-curable film adhesive is used, and the workpiece with the cured adhesive obtained by cutting it by irradiating it with laser light and curing it with energy rays can be properly picked up from the support sheet.

[0217] <Method for manufacturing a semiconductor chip with a cured adhesive (manufacturing method (2-1))> The manufacturing method (2) when the workpiece is a semiconductor wafer is a manufacturing method of a semiconductor chip with a cured adhesive using the film-like adhesive composite sheet, the gel fraction of the energy ray-cured product of the film-like adhesive in the film-like adhesive composite sheet is 13% or less; The manufacturing method (2) includes an energy ray curing step (sometimes referred to in this specification as "energy ray curing step (2-1)") of using a semiconductor chip group holder in which a plurality of semiconductor chips are aligned on the surface of the film-like adhesive in the film-like adhesive composite sheet opposite the support sheet side and are held by the backside of the semiconductor chips, and curing the film-like adhesive in the semiconductor chip group holder with energy rays to produce a cured semiconductor chip group holder in which a plurality of the semiconductor chips are aligned and held on the energy ray-cured product of the film-like adhesive; a cutting step (sometimes referred to in this specification as "cutting step (2-1)") in which, after the energy ray curing step, a laser beam is applied to the energy ray-cured product of the film-like adhesive that is exposed between the semiconductor chips in the cured semiconductor chip group holder, thereby cutting the energy ray-cured product along the semiconductor chips, thereby producing semiconductor chips with an adhesive-cured product that include the semiconductor chips and the cut energy ray-cured product provided on the back surface of the semiconductor chips; After the cutting step, a pick-up step (sometimes referred to in this specification as "pick-up step (2-1)") is performed to separate the semiconductor chip with the adhesive cured product from the support sheet and pick it up (this manufacturing method is sometimes referred to in this specification as "manufacturing method (2-1)").

[0218] The manufacturing method (2-1) will be described below with reference to the drawings. 5 is a cross-sectional view for schematically explaining an example of the manufacturing method (2-1). Here, the manufacturing method (2-1) will be explained using the film-like adhesive composite sheet 101 shown in FIG. However, the film-like adhesive composite sheet 101 used in manufacturing method (2-1) differs from the film-like adhesive composite sheet 101 used in manufacturing method (2-1) in that the gel fraction of the energy ray-cured product of the film-like adhesive 13 therein is limited to 13% or less.

[0219] [Energy ray curing process (2-1)] In the energy ray curing step (2-1) of the manufacturing method (2-1), first, a semiconductor chip group holder 901 as shown in FIG. 5(a) is prepared. The semiconductor chip group holder 901 used here differs from the semiconductor chip group holder 901 used in the cutting step (1-1) described above only in that the gel fraction of the energy ray-cured product of the film-like adhesive 13 therein is limited to 13% or less. The gel fraction of the energy ray-cured product of the film-like adhesive 13 in the semiconductor chip group holder 901 used in the cutting step (1-1) is not particularly limited and may be 13% or less or may exceed 13%. Therefore, further explanation of the semiconductor chip group holder 901 used in the manufacturing method (2-1) will be omitted.

[0220] In the energy ray curing step (2-1) of the manufacturing method (2-1), as shown in Figure 5(b), the film-like adhesive 13 in the semiconductor chip group holder 901 is cured with energy rays to produce a cured semiconductor chip group holder 904 in which multiple semiconductor chips 90 are aligned and held on the energy ray-cured product 132 of the film-like adhesive. The first surface 132a and the second surface 132b of the energy ray-cured film adhesive 132 originate from the first surface 13a and the second surface 13b of the film adhesive 13, respectively.

[0221] The energy ray irradiation conditions (illuminance, amount of light) when the film adhesive 13 is cured with energy ray are the same as those in the energy ray curing step (1-1) described above.

[0222] [Cutting process (2-1)] After the energy ray curing step (2-1) of the manufacturing method (2-1), in the cutting step (2-1), as shown in Figure 5 (c), laser light R is irradiated onto the energy ray cured product 132 of the film-like adhesive exposed between the semiconductor chips 90 in the cured semiconductor chip group holder 904, and the energy ray cured product 132 of the film-like adhesive is cut along the semiconductor chips 90. 5(d), a semiconductor chip 93 with an adhesive-cured product is produced, which includes the semiconductor chip 90 and the cut energy ray-cured product 133 of the film-like adhesive provided on the back surface 90b of the semiconductor chip 90. These multiple semiconductor chips 93 with the adhesive-cured product are aligned and held on the support sheet 10 (in other words, the base material 11), and together with the support sheet 10, constitute a group 905 of semiconductor chips with an adhesive-cured product. The first surface 133a and the second surface 133b of the cut energy ray-cured film adhesive product 133 originate from the first surface 132a and the second surface 132b, respectively, of the energy ray-cured film adhesive product 132 before cutting.

[0223] In this specification, the "energy ray-cured film adhesive product that has been cut" may be simply referred to as the "energy ray-cured film adhesive product", not limited to the case of production method (2-1).

[0224] The semiconductor chip 93 with the cured adhesive is the same as the semiconductor chip 92 with the cured adhesive produced in the energy ray curing process (1-1) described above, or even if it is different, the difference is minor and it is substantially the same as the semiconductor chip 92 with the cured adhesive.

[0225] The irradiation conditions of the laser light R when cutting the energy ray-cured film adhesive 132 are the same as those when cutting the film adhesive 13 in the above-mentioned cutting step (1-1).

[0226] By using the film-like adhesive 13, typically, no contaminants originating from the energy ray-cured product 132 of the film-like adhesive are found on the surfaces (first surfaces 90a, side surfaces, etc.) of the semiconductor chips 90 in the group 905 of semiconductor chips with the cured adhesive obtained by the cutting process (2-1), and contamination of the semiconductor chips 90 is suppressed.

[0227] [Pickup process (2-1)] After the cutting step (2-1) of the manufacturing method (2-1), in the picking up step (2-1), the semiconductor chip 93 with the cured adhesive attached thereto is separated from the support sheet 10 and picked up, as shown in FIG. 5(e). This allows the desired semiconductor chip 93 with the cured adhesive to be taken out.

[0228] In the pick-up step (2-1), peeling occurs between the second surface 133b of the energy ray-cured product 133 of the film-like adhesive in the semiconductor chip 93 with the adhesive-cured product and the first surface 10a of the support sheet 10. In the pick-up process (2-1), by using the film-like adhesive 13, it is not difficult to peel off the energy ray cured product (cured adhesive product) 133 of the film-like adhesive from the support sheet 10, and the semiconductor chip 93 with the cured adhesive product can be picked up normally from the support sheet 10.

[0229] The semiconductor chip 93 with the cured adhesive attached thereto can be picked up in the same manner as the semiconductor chip 92 with the cured adhesive attached thereto in the above-mentioned pick-up step (1-1).

[0230] <<Modification of the manufacturing method of a workpiece with a cured adhesive>> The method for manufacturing a workpiece with a cured adhesive of this embodiment may or may not include other processes that do not fall under any of the cutting process, the energy ray curing process, and the pick-up process, as long as the effects of the present invention are not impaired. The other steps can be selected arbitrarily depending on the purpose, and further can be selected arbitrarily depending on the type of film-like adhesive composite sheet or workpiece, and are not particularly limited. The timing of performing the other steps can be appropriately selected depending on the contents of the other steps.

[0231] Up to this point, the manufacturing method has been described using the film-like adhesive composite sheet 101 shown in Figure 2, but in the manufacturing method of this embodiment for a workpiece with a cured adhesive material, other film-like adhesive composite sheets may also be used. When using the other film-like adhesive composite sheet, based on the difference in configuration between the other film-like adhesive composite sheet and the film-like adhesive composite sheet 101 shown in Figure 2, the manufacturing method of the present embodiment for producing a workpiece with a cured adhesive material may include one or more of the other steps performed at any time.

[0232] When using the other film-like adhesive composite sheet, based on the difference in configuration between the other film-like adhesive composite sheet and the film-like adhesive composite sheet 101 shown in Figure 2, the implementation mode of at least one of the cutting process, the energy ray curing process, and the pick-up process in the manufacturing method (1) and the manufacturing method (2) may be changed within the scope of the intent of the present invention, and the other process may be included.

[0233] For example, when the film-like adhesive composite sheet 102 shown in FIG. 3 is used, the semiconductor chip with the cured adhesive attached is peeled from the intermediate release layer 14, not from the substrate 11, in the pick-up step.

[0234] ◇ Manufacturing method of substrate device (method of using workpiece with adhesive cured material) A substrate device can be manufactured using the workpiece with the cured adhesive obtained by the above-described manufacturing method. The substrate device can be manufactured by a known method, except for the use of the workpiece with the cured adhesive material described above. For example, a workpiece with a cured adhesive can be mounted on a circuit board by adhering it to the circuit board using the cured adhesive (the energy ray-cured film-like adhesive) therein (mounting process). If the film-like adhesive is thermosetting, the energy ray-cured film-like adhesive after mounting can be further thermally cured to more firmly fix the workpiece to the circuit board. The energy ray-cured film-like adhesive may be thermally cured at the same time as the workpiece is heated when it is sealed on the circuit board with resin. In addition to mounting the workpiece on the circuit board, other processes may be added as necessary to manufacture the desired substrate device. [Example]

[0235] The present invention will be described in more detail below with reference to specific examples, although the present invention is not limited to the examples shown below.

[0236] <<Raw materials for resin manufacturing>> The full names of the raw materials for producing the resins, which are abbreviated in the examples and comparative examples, are shown below. MA: methyl acrylate HEA: 2-hydroxyethyl acrylate BA: n-butyl acrylate GMA: Glycidyl methacrylate

[0237] <<Raw materials for manufacturing adhesive compositions>> The raw materials used in the production of the adhesive composition are listed below. [Polymer component (a)] (a)-1: An acrylic resin (weight average molecular weight: 400,000, glass transition temperature: 6°C) obtained by copolymerizing MA (85 parts by mass) and HEA (15 parts by mass). (a)-2: Acrylic resin ("Teisan Resin (registered trademark) SG-P3" manufactured by Nagase ChemteX Corporation) (a)-3: Acrylic resin (weight average molecular weight 900,000, glass transition temperature −28° C.) obtained by copolymerizing BA (55 parts by mass), MA (10 parts by mass), GMA (20 parts by mass), and HEA (15 parts by mass). [Epoxy resin (b1)] (b1)-1: Dicyclopentadiene type epoxy resin (Nippon Kayaku Co., Ltd. "XD-1000", softening point 68-78°C, epoxy equivalent 245-260g / eq) (b1)-2: A mixture of liquid bisphenol F epoxy resin and acrylic rubber particles (Nippon Shokubai Co., Ltd. "Acryset (registered trademark) BPF307", epoxy equivalent 235 g / eq) (b1)-3: Solid triphenylene epoxy resin (Nippon Kayaku Co., Ltd. "EPPN-502H", epoxy equivalent 158 ​​to 178 g / eq) (b1)-4: A mixture of liquid bisphenol A epoxy resin and acrylic rubber particles (Nippon Shokubai Co., Ltd. "Acryset (registered trademark) BPA328", epoxy equivalent 235 g / eq) [Thermal curing agent (b2)] (b2)-1: Dicyandiamide (ADEKA Corporation, "ADEKA HARDNER (registered trademark) EH-3636AS", solid dispersion type latent curing agent, softening point 209°C, hydroxyl group equivalent 21 g / eq) (b2)-2: Novolac phenolic resin (Showa Denko K.K. "Shounol (registered trademark) BRG-556", hydroxyl group equivalent 104 g / eq) [Curing accelerator (c)] (c)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezol (registered trademark) 2PHZ-PW" manufactured by Shikoku Chemicals Corporation) [Filler (d)] (d)-1: Spherical silica ("Adma Fine (registered trademark) SC2050" manufactured by Admatechs Co., Ltd.) [Coupling agent (e)] (e)-1: A silicate compound to which 3-glycidoxypropyltrimethoxysilane has been added ("MKC (registered trademark) Silicate MSEP-2" manufactured by Mitsubishi Chemical Corporation) [Energy ray curable component (g)] (g)-1: Tricyclodecanedimethylol diacrylate ("KAYARAD (registered trademark) R-684" manufactured by Nippon Kayaku Co., Ltd., molecular weight 304) [Photopolymerization initiator (h)] (h)-1: 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one ("IRGACURE® 127" manufactured by Ciba Specialty Chemicals) (h)-2: 1-Hydroxycyclohexyl phenyl ketone ("IRGACURE(R) 184" manufactured by Ciba Specialty Chemicals)

[0238] [Example 1] <<Manufacturing of film adhesives>> <Production of Adhesive Composition> The components shown in Table 1 were dissolved or dispersed in methyl ethyl ketone to the amounts shown in Table 1, and the mixture was stirred at 23°C to produce a thermosetting adhesive composition in which the total concentration of all components other than the solvent was 50 mass%.

[0239] <Production of film adhesive> A release film (second release film, "SP-PET502150" manufactured by Lintec Corporation, thickness 50 μm) made of polyethylene terephthalate, one side of which had been treated for release by silicone treatment, was used. The adhesive composition obtained above was applied to the release-treated surface and dried at 100°C for 1 minute to produce film-like adhesives having both energy ray-curability and thermosetting properties, with thicknesses of 5 μm and 40 μm, respectively. Hereinafter, in this specification, these film-like adhesives may be referred to as "film-like adhesive (f1)". Furthermore, the release-treated surface of a separate release film (first release film, "SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) was bonded to the exposed surface of the obtained film adhesive (film adhesive (f1)) that did not have the second release film, thereby producing a film adhesive with a release film, which was composed of the film adhesive, a first release film provided on one side of the film adhesive, and a second release film provided on the other side of the film adhesive.

[0240] <<Evaluation of film adhesives>> <Measurement of gel fraction of film adhesive> The first release film and the second release film were removed from the film adhesive (thickness 40 μm) obtained above, and the film adhesive was cut into a piece measuring 50 mm × 100 mm. This piece was then wrapped in a nylon mesh sheet (mesh size 200) measuring 100 mm × 150 mm and stapled together to form a measurement sample. The mass M of the measurement sample was measured using a precision balance. 11 The mass of the nylon mesh sheet, M2, and the mass of the staples, M3, were weighed. Next, the measurement sample was immersed in methyl ethyl ketone (100 mL) at 25°C for 24 hours, after which the insoluble portion of the slice (film adhesive), the nylon mesh sheet, and the staples were all removed, dried at 90°C for 3 hours, and then left to stand at 23°C and a relative humidity of 50% for 1 hour to condition the humidity. Next, the mass M of the measurement sample after immersion, drying and humidity conditioning 51 (i.e., the total mass of the insoluble portion of the slice, the mass of the nylon mesh sheet, and the mass of the staples) was weighed using a precision balance. The gel fraction of the components of the film-like adhesive other than the filler (d) was then calculated using the following formula (i). Here, the mass M4 of the filler (d) is 0. The results are shown in the column "Gel fraction (%) of film-like adhesive" in Table 1. [Gel fraction of film adhesive] = (M 51 -M2-M3-M4) / (M 11 -M2-M3-M4) x 100 (i)

[0241] <Measurement of gel fraction of energy ray cured film adhesive> The first release film and the second release film were removed from the film adhesive (thickness 40 μm) obtained above, and the film adhesive was irradiated with an ultraviolet ray irradiation device ("RAD2010" manufactured by Lintec Corporation) equipped with a high-pressure mercury lamp at an illuminance of 230 mW / cm in an air atmosphere. 2 , light intensity 190mJ / cm 2 The film adhesive was cured by irradiating it with ultraviolet light under the conditions of Next, the UV-cured film adhesive thus obtained was cut into a piece measuring 50 mm x 100 mm, and this piece was wrapped in a nylon mesh sheet (mesh size 200) measuring 100 mm x 150 mm and stapled together to prepare a measurement sample. The mass M of the measurement sample was measured using a precision balance. 21 The mass of the nylon mesh sheet, M2, and the mass of the staples, M3, were weighed. Thereafter, the mass M of the measurement sample obtained here after immersion in methyl ethyl ketone, drying, and humidity conditioning was measured in the same manner as for the measurement sample when measuring the gel fraction of the above-mentioned film-like adhesive. 52 (i.e., the total mass of the insoluble portion of the slice, the mass of the nylon mesh sheet, and the mass of the staples) was weighed on a precision balance, and the gel fraction of the components other than filler (d) in the UV-cured film-like adhesive was calculated using the following formula (ii). Here, the mass M4 of filler (d) is 0. The results are shown in the column "Gel fraction (%) of energy ray-cured film-like adhesive" in Table 1. [Gel fraction of film adhesive] = (M 52 -M2-M3-M4) / (M 21 -M2-M3-M4) x 100 (ii)

[0242] <Film adhesive G 23 Measurement of '> A laminate of film-like adhesives (thickness: 1000 μm) was produced by using multiple sheets of the film-like adhesive with release film obtained above (thickness of film-like adhesive: 40 μm), removing the first release film and the second release film, and repeatedly bonding the exposed surfaces of the film-like adhesives together. Next, a piece having a circular planar shape was punched out from the laminate, and this was used as a test piece (t1) (diameter 8 mm, thickness 1000 μm). Using a shear viscosity measuring device ("MCR301" manufactured by Anton Paar), the test piece (t1) was heated from -10°C to 50°C at a heating rate of 4°C / min. Within this temperature range, the generated shear strain was increased stepwise in the range of 0.01 to 10% under the condition of a measurement frequency of 1Hz. The shear storage modulus (G 23 The results are shown in Table 1.

[0243] <G of energy ray cured film adhesive 23 Measurement of '> The above film adhesive G 23 A laminate of film-like adhesive (thickness 1000 μm) was prepared in the same manner as in the measurement of '. Next, under a nitrogen gas atmosphere, the laminate was irradiated with ultraviolet light at an illuminance of 230 mW / cm using an ultraviolet irradiation device equipped with a high-pressure mercury lamp ("RAD2010" manufactured by Lintec Corporation). 2 , light intensity 190mJ / cm 2 The laminate (film-like adhesive) was cured by irradiating it with ultraviolet light under the conditions above. Next, a circular piece having a planar shape was punched out from the laminate after ultraviolet irradiation, and this was used as a test piece (t2) (diameter 8 mm, thickness 1000 μm). Hereafter, the above film adhesive G 23 The shear storage modulus (G 23 The results are shown in Table 1.

[0244] <<Manufacturing of film-type adhesive composite sheets>> The first release film was removed from the film-like adhesive with release film obtained above (film-like adhesive thickness: 5 μm). A film-like adhesive composite sheet was produced by using a support sheet (support sheet consisting of only a substrate) (s1) (thickness 80 μm) and laminating the exposed surface of the film-like adhesive opposite the side with the second release film to one side of the support sheet. This film-like adhesive composite sheet is a film-like adhesive composite sheet with a release film, constructed by laminating a support sheet consisting of only a substrate, a film-like adhesive, and a second release film in this order in the thickness direction. The support sheet (s1) has a three-layer structure consisting of a linear low-density polyethylene layer, a polypropylene layer, and a linear low-density polyethylene layer.

[0245] <<Production of silicon chips with cured adhesive, and evaluation of film-type adhesive composite sheets and film-type adhesives>> <Evaluation of the effect of film adhesive in suppressing contamination of silicon chips when cutting> (Fabrication of silicon chip group holder) Using a half-cut dicer (DISCO Corporation, "DFG6363"), half-cuts were made to form grooves at an interval of 8 mm in two mutually perpendicular directions from the surface of the silicon wafer to a distance partway in the thickness direction. A backgrinding tape ("Adwill E-3125KN" manufactured by Lintec Corporation) was attached to the surface of the half-cut silicon wafer where the grooves were formed, and the backside of the silicon wafer was ground using a polishing machine ("DFG8761" manufactured by Disco Corporation). Finally, the ground surface was dry polished to make the thickness of the non-grooved part of the silicon wafer 50 μm, and grooves were made to appear on the ground surface of the silicon wafer. The silicon wafer was then divided at the grooves to produce silicon chips (8 mm x 8 mm).

[0246] The second release film was removed from the film-like adhesive composite sheet obtained above, and the exposed surface of the film-like adhesive was attached to the backside (ground surface) of the group of silicon chips obtained above (silicon chip group). Next, the backgrinding tape was irradiated with ultraviolet light to cure the adhesive layer in the backgrinding tape, and the backgrinding tape was removed from the group of silicon chips. As a result of the above, a silicon chip group holder was produced in which multiple silicon chips were aligned and held on the surface of the film adhesive in the film adhesive composite sheet opposite the support sheet side.

[0247] (Preparation of silicon chips with film adhesive) Using the silicon chip group holder obtained above, the film adhesive exposed between the silicon chips was irradiated with laser light to cut the film adhesive along the silicon chips. A DISCO laser dicer "DFL7160" was used, and the laser light was irradiated to a depth of 20 μm from the surface of the film adhesive under conditions of a laser wavelength of 355 nm, an output of 0.4 W, and a feed rate of 200 mm / s. This produced a silicon chip with a film adhesive, which included a silicon chip and the cut film adhesive on the backside of the silicon chip (cutting step (1-1)). These multiple silicon chips with a film adhesive were aligned and held on a support sheet (s1), and together with the support sheet (s1), constituted a silicon chip group with a film adhesive.

[0248] (Evaluation of the effect of film adhesive on preventing contamination of silicon chips when cutting) The group of silicon chips with film-like adhesive obtained above were observed using an optical microscope (Keyence Corporation, "VHX-100") to confirm the degree of adhesion of contaminants originating from the film-like adhesive to the surface of the silicon chip. The effect of inhibiting contamination of the silicon chip when the film-like adhesive was cut was then evaluated according to the following criteria. The results are shown in the "Effect of inhibiting contamination of silicon chips" column in Table 1. A: No contaminants were found on the surface of the silicon chip, and the effect of suppressing contamination of the silicon chip was confirmed. B: Contaminants were observed on the surface of the silicon chip, and no effect of suppressing contamination of the silicon chip was observed.

[0249] <Evaluation of pick-up ability of silicon chips with cured adhesive> (Preparation of silicon chips with cured adhesive) The film adhesive in the group of silicon chips with film adhesive that was used to evaluate the effect of suppressing contamination of the silicon chips was irradiated with an ultraviolet ray irradiation device ("RAD2010" manufactured by Lintec Corporation) equipped with a high-pressure mercury lamp at an illuminance of 230 mW / cm in an air atmosphere. 2 , light intensity 190mJ / cm 2 The film-like adhesive was UV-cured by irradiating it with UV rays under the conditions of

[0045] . As a result, a plurality of silicon chips with adhesive-cured material were produced on the support sheet (s1), each comprising a silicon chip and a UV-cured product of the film-like adhesive provided on the back surface of the silicon chip (energy ray curing step (1-1)). These plurality of silicon chips with adhesive-cured material were aligned and held on the support sheet (s1), and together with the support sheet (s1), constituted a group of silicon chips with adhesive-cured material.

[0250] (Manufacturing silicon chips with cured adhesive) Using a pick-up die bonding machine (Canon Machinery's "BESTEM D-510"), a silicon chip with cured adhesive from the group of silicon chips with cured adhesive was picked up by detaching it from the support sheet (s1) in an attempt to obtain the desired silicon chip with cured adhesive (pick-up process (1-1)). This pick-up was performed on a total of five silicon chips with cured adhesive, randomly selected, with the pin push-up speed set to 5 mm / s and the pin push-up height set to 200 μm, and five pins were used to push up one silicon chip with cured adhesive from the support sheet (s1).

[0251] (Evaluation of pick-up ability of silicon chips with cured adhesive) After the above pick-up step (1-1), the pick-up properties of the silicon chip with the cured adhesive were evaluated according to the following criteria. The results are shown in the "Pick-up properties" column in Table 1. [Evaluation criteria] A: Five silicon chips with cured adhesive were successfully picked up. B: 1 to 4 silicon chips with cured adhesive were successfully picked up. C: Five silicon chips with cured adhesive could not be picked up properly.

[0252] <Measurement of peel strength between energy ray-cured film adhesive and support sheet> A rectangular piece measuring 25 mm x 250 mm was cut out from the film-like adhesive composite sheet with a release film obtained above. Next, the section was irradiated with 230 mW / cm from the support sheet side. 2 , light intensity 190mJ / cm 2 By irradiating ultraviolet light under the conditions above, the film adhesive in the slice was cured by ultraviolet light, and a test piece (t3) with a release film was prepared.

[0253] Next, double-sided tape was attached to one side of a rigid support made of a polystyrene plate, and the release film was removed from the test piece (t3). The exposed surface of the UV-cured film adhesive in the test piece (t3) was then attached to the exposed surface of the double-sided tape (the surface opposite to the surface attached to the rigid support). At this time, the entire exposed surface of the UV-cured film adhesive was attached to the exposed surface of the double-sided tape. In an environment of a temperature of 23°C and a relative humidity (RH) of 50%, a rubber roller having a mass of 2 kg was moved back and forth once on the hard support of the resulting laminate of the hard support, the double-sided tape, and the test piece (t3), thereby pressing the laminate and fixing the test piece (t3) to one side of the hard support via the double-sided tape.

[0254] Next, this test piece (t3) was fixed to a hard support and then allowed to stand for 30 minutes in an environment at a temperature of 23°C and a relative humidity (RH) of 50%. Next, using a universal tensile tester (Shimadzu Corporation, "Autograph AG-IS"), the support sheet (s1) was peeled from the UV-cured film-like adhesive in the test piece (t3). A peel test (180° peel) was performed in which the support sheet (s1) was peeled from the UV-cured film-like adhesive in its longitudinal direction at a peeling speed of 300 mm / min, with the angle between the surface of the UV-cured film-like adhesive to which the support sheet (s1) was attached being 180°. The peel force measured at this time was used as the peel force between the UV-cured film-like adhesive and the support sheet. The results are shown in the "Peel Force (mN / 25 mm)" column in Table 1.

[0255] <<Production and evaluation of film-type adhesives, production of silicon chips with cured adhesives, and production and evaluation of film-type adhesive composite sheets>> [Examples 2 to 3] Film-like adhesives and film-like adhesive composite sheets were produced and evaluated in the same manner as in Example 1, except that the amounts of the components blended were changed during the production of the adhesive composition so that the types and contents of the components contained in the film-like adhesive were as shown in Table 1. The results are shown in Table 1. Hereinafter, in this specification, the film adhesive obtained in Example 2 may be referred to as "film adhesive (f2)," and the film adhesive obtained in Example 3 may be referred to as "film adhesive (f3)."

[0256] In Table 1, a "-" in the "Components (content (parts by mass))" column means that the film adhesive does not contain that component. This also applies to the other tables that follow.

[0257] [Example 4] Using the film-like adhesive composite sheet obtained in Example 1, silicon chips with cured adhesive were manufactured by changing the timing of ultraviolet irradiation from after laser light irradiation to before laser light irradiation (switching the order of ultraviolet light irradiation and laser light irradiation), unlike in Example 1. More specifically, this is as follows.

[0258] <<Evaluation of film adhesive composite sheets>> <Evaluation of the contamination suppression effect on silicon chips when cutting energy ray-cured film adhesives> (Fabrication of silicon chip group holder) A silicon chip group holder was produced in the same manner as in Example 1.

[0259] (Preparation of a hardened silicon chip group holder) The film adhesive (film adhesive (f1)) in the silicon chip group holder obtained above was irradiated with an ultraviolet ray irradiation device ("RAD2010" manufactured by Lintec Corporation) equipped with a high-pressure mercury lamp at an illuminance of 230 mW / cm in an air atmosphere. 2, light intensity 190mJ / cm 2 The film-like adhesive was UV-cured by irradiating it with UV rays under the conditions of

[0043] 2. As a result, a cured silicon chip group holder was produced in which a plurality of silicon chips were aligned and held on the UV-cured film-like adhesive (energy ray curing step (2-1)).

[0260] (Preparation of silicon chips with cured adhesive) Using the cured silicon chip group holder obtained above, the UV-cured film-like adhesive exposed between the silicon chips was irradiated with laser light under the same conditions as in Example 1, thereby cutting the UV-cured film-like adhesive along the silicon chips. This produced a silicon chip with a cured adhesive, which included a silicon chip and the cut UV-cured product provided on the back surface of the silicon chip (cutting step (2-1)). These multiple silicon chips with the cured adhesive were aligned and held on a support sheet (s1), and together with the support sheet (s1), constituted a silicon chip group with a cured adhesive.

[0261] (Evaluation of the contamination suppression effect on silicon chips when cutting an energy ray-cured film adhesive) For the group of silicon chips with the cured adhesive obtained above, the degree of adhesion of contaminants originating from the UV-cured film adhesive to the surface of the silicon chip was confirmed using the same method as in Example 1. Then, using the same method as in Example 1, the effect of inhibiting contamination of the silicon chip when cutting the UV-cured film adhesive was evaluated. The results are shown in the column "Effect of inhibiting contamination of silicon chip" in Table 1.

[0262] <Evaluation of pick-up ability of silicon chips with cured adhesive> (Manufacturing silicon chips with cured adhesive) Using the group of silicon chips with cured adhesive obtained above, an attempt was made to obtain the desired silicon chips with cured adhesive by separating and picking up the silicon chips with cured adhesive from the support sheet (s1) in the group of silicon chips with cured adhesive in the same manner as in Example 1 (pick-up step (2-1)).

[0263] (Evaluation of pick-up ability of silicon chips with cured adhesive) After the above pick-up step (2-1), the pick-up properties of the silicon chip with the cured adhesive were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0264] In Table 1, the timing of ultraviolet irradiation during the production of the silicon chip with the cured adhesive is indicated by the symbol "*" as to whether it was before or after the laser light irradiation.

[0265] [Example 5] <<Production and evaluation of film adhesives>> Film-like adhesives were produced and evaluated in the same manner as in Example 1, except that the types and amounts of the components blended were changed during the production of the adhesive composition so that the types and contents of the components contained in the film-like adhesive were as shown in Table 2. The results are shown in Table 2. Hereinafter, in this specification, the film adhesive obtained in this example may be referred to as "film adhesive (4)."

[0266] <<Production and Evaluation of Film-Type Adhesive Composite Sheets>> A film-like adhesive composite sheet was produced and evaluated in the same manner as in Example 1, except that a different type of support sheet (s2) (70 μm thick) consisting of only a substrate was used instead of the support sheet (s1). The support sheet (s2) has a single-layer structure consisting of a linear low-density polyethylene layer. The results are shown in Table 2.

[0267] [Comparative Example 1] <<Production and evaluation of film adhesives>> Film-like adhesives were produced and evaluated in the same manner as in Example 1, except that the types and amounts of the components blended were changed during the production of the adhesive composition so that the types and contents of the components contained in the film-like adhesive were as shown in Table 2. The results are shown in Table 2. Hereinafter, in this specification, the film adhesive obtained in this comparative example may be referred to as "film adhesive (fR1)."

[0268] <<Production and Evaluation of Film-Type Adhesive Composite Sheets>> A film adhesive composite sheet was produced and evaluated in the same manner as in Example 1, except that the film adhesive (fR1) obtained above was used instead of the film adhesive (f1). The results are shown in Table 2.

[0269] Comparative Example 2 <<Production and Evaluation of Film-Type Adhesive Composite Sheets>> A film adhesive composite sheet was produced and evaluated in the same manner as in Example 4, except that the film adhesive (f1) was replaced with the film adhesive obtained in Comparative Example 1 (film adhesive (fR1)). The results are shown in Table 2.

[0270] Comparative Example 3 <<Evaluation of film adhesives>> A die bonding film identical to the die bonding film constituting a commercially available dicing die bonding sheet ("Adwill LE5000" manufactured by Lintec Corporation) was separately prepared. This dicing die bonding sheet comprises a dicing sheet and a die bonding film provided on one side of the dicing sheet, and corresponds to a film-like adhesive composite sheet. The dicing sheet and the die bonding film correspond to a support sheet and a film-like adhesive, respectively. The die bonding film was evaluated in the same manner as when the film-like adhesive of Example 1 was evaluated. The results are shown in Table 3. The dicing sheet in the dicing die bonding sheet is mainly composed of linear low-density polyethylene, and the die bonding film is energy ray curable.

[0271] <<Evaluation of film adhesive composite sheets>> The dicing die bonding sheet was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0272] <<Evaluation of film adhesive composite sheets>> Comparative Example 4 The dicing die bonding sheet used in Comparative Example 3 was evaluated in the same manner as in Example 4. The results are shown in Table 3.

[0273] [Reference example 1] The film-like adhesive composite sheet was evaluated in the same manner as in Example 4, except that the silicon chip group holder produced in Example 2 was used instead of the silicon chip group holder produced in Example 4. The results are shown in Table 3.

[0274] [Reference example 2] The film-like adhesive composite sheet was evaluated in the same manner as in Example 4, except that the silicon chip group holder produced in Example 3 was used instead of the silicon chip group holder produced in Example 4. The results are shown in Table 3.

[0275] [Table 1]

[0276] [Table 2]

[0277] [Table 3]

[0278] As is clear from the above results, in Examples 1 to 3 and 5, the film adhesive was cut by irradiation with laser light, and then cured with energy rays, and the resulting silicon chip with the cured adhesive could be successfully picked up from the support sheet. In Examples 1 to 3 and 5, the film adhesive was found to have an effect of suppressing contamination of the silicon chip when it was cut, and this result was consistent with the good pick-up properties in these Examples as described above. In Examples 1 to 3 and 5, the peel force between the UV-cured film adhesive and the support sheet was 80 mN / 25 mm, which was small within an appropriate range. This result was also consistent with the good pickup properties in these Examples, as described above. In Examples 1 to 3 and 5, the gel fraction of the film adhesive was 12% or less.

[0279] In Examples 1 to 3 and 5, the film adhesive G 23 ' was below 0.25 MPa. The film adhesives of Examples 1 to 3 and 5 did not contain the filler (d). In the film adhesives of Examples 1 to 3 and 5, the content of polymer component (a) relative to the total mass of the film adhesive was 28 mass % or less.

[0280] The film adhesive used in Example 4 was the same as the film adhesive used in Example 1. In Example 4, the film adhesive was cured with energy rays to form a cured product, and then this energy ray-cured product was cut by irradiation with laser light, and the resulting silicon chip with the cured adhesive could be successfully picked up from the support sheet. That is, the film adhesives of Examples 1 and 4 enabled normal pick-up of silicon chips with cured adhesive regardless of whether the timing of energy ray irradiation was before or after laser light irradiation. In Examples 1 and 4, the gel fraction of the UV-cured film adhesive was 13%.

[0281] In contrast, in Comparative Examples 1 and 3, after the film adhesive was cut by irradiation with laser light and then cured with energy rays, none of the five silicon chips with cured adhesive obtained could be picked up normally from the support sheet. In Comparative Examples 1 and 3, the film adhesive was not found to have any effect in suppressing contamination of the silicon chip when it was cut, and this result was consistent with the poor pickup properties of these Comparative Examples as described above. In particular, in Comparative Example 3, the peel force between the UV-cured film adhesive and the support sheet was as high as 100 mN / 25 mm, which was consistent with the poor pickup properties of this Comparative Example, as described above. In Comparative Examples 1 and 3, the gel fraction of the film adhesive was high, at 25% or more.

[0282] The film-like adhesive used in Comparative Example 2 was the same as the film-like adhesive used in Comparative Example 1, and the film-like adhesive used in Comparative Example 4 was the same as the film-like adhesive used in Comparative Example 3. In Comparative Examples 2 and 4, the film-like adhesive was cured with energy rays to form a cured product, and then this energy ray-cured product was cut by irradiation with laser light, and then none of the five silicon chips with the cured adhesive thus obtained could be properly picked up from the support sheet. That is, when the film-like adhesives of Comparative Examples 2 and 4 were used, it was difficult to pick up the silicon chip with the cured adhesive attached, regardless of whether the timing of the energy ray irradiation was before or after the laser light irradiation. In Comparative Example 2, the gel fraction of the UV-cured film-like adhesive was the same as in Comparative Example 1, and in Comparative Example 4, the gel fraction of the UV-cured film-like adhesive was the same as in Comparative Example 3, both of which were high.

[0283] The film-like adhesive used in Reference Example 1 was the same as the film-like adhesive used in Example 2. In Reference Example 1, the film-like adhesive was cured with energy rays to form a cured product, and then this energy ray-cured product was cut by irradiation with laser light, and then five silicon chips with the cured adhesive thus obtained could not all be picked up normally from the support sheet. In Reference Example 1, the gel fraction of the UV-cured film adhesive was 19%.

[0284] The film-like adhesive used in Reference Example 2 was the same as the film-like adhesive used in Example 3. In Reference Example 2, the film-like adhesive was cured with energy rays to form a cured product, and then this energy ray-cured product was cut by irradiation with laser light, and then five silicon chips with the cured adhesive thus obtained could not all be picked up normally from the support sheet. In Reference Example 2, the gel fraction of the UV-cured film adhesive was 15%. [Industrial Applicability]

[0285] The present invention can be used in the manufacture of substrate devices. [Explanation of symbols]

[0286] 10, 20... Support sheet, 10a, 20a... First surface of support sheet 101, 102... Film-like adhesive composite sheet 11...Base material 13,130···Film adhesive, 13a···First surface of film adhesive 131,132,133... Energy ray cured film adhesive 90: Semiconductor chip; 90b: Back surface of semiconductor chip 901: Semiconductor chip group holder 904: Hardened semiconductor chip group holder 91 Semiconductor chip with film adhesive 92, 93...Semiconductor chip with cured adhesive R...Laser light

Claims

1. A film-like adhesive having energy ray curability and a gel fraction of 13% or less.

2. A test piece (t1) having a thickness of 1000 μm and constructed by laminating a plurality of sheets of the film-like adhesive was used, and the shear strain generated in the test piece (t1) was increased in the range of 0.01 to 10% under the condition of a measurement frequency of 1 Hz in the temperature range of -10 ° C to 50 ° C., and the shear storage modulus G of the test piece (t1) at a shear strain of 1% at a temperature of 23 ° C. ２３ When the shear storage modulus G ２３ 2. The film adhesive according to claim 1, wherein the modulus of elasticity is 8 MPa or less.

3. The film-like adhesive according to claim 1 or 2, wherein the content of the filler (d) in the film-like adhesive is less than 15 mass % relative to the total mass of the film-like adhesive.

4. 3. The film-like adhesive according to claim 1, wherein the content of the polymer component (a) in the film-like adhesive is 28 mass % or less relative to the total mass of the film-like adhesive.

5. 3. The film-like adhesive according to claim 1, wherein the energy ray-cured product of the film-like adhesive has a gel fraction of 13% or less.

6. A support sheet and a film-like adhesive provided on one surface of the support sheet, A film-like adhesive composite sheet, wherein the film-like adhesive is the film-like adhesive according to claim 1.

7. 7. The film-like adhesive composite sheet according to claim 6, wherein the support sheet consists of only a substrate.

8. The film-like adhesive composite sheet had an illuminance of 230 mW / cm ２ , light intensity 190mJ / cm ２ A test piece (t3) having a width of 25 mm was prepared by curing the film-like adhesive with ultraviolet light under the conditions of 8. The film-like adhesive composite sheet according to claim 6 or 7, wherein when a peel test is performed in which the support sheet is peeled from the UV-cured film-like adhesive of the test piece (t3), and the support sheet is peeled from the UV-cured film-like adhesive in its length direction at a peel speed of 300 mm / min, with the angle between the surface of the UV-cured product to which the support sheet was attached and the surface of the support sheet to which the UV-cured product was attached being 180°, the peel force between the UV-cured film-like adhesive and the support sheet is 100 mN / 25 mm or less.

9. A method for producing a workpiece with a cured adhesive using the film-like adhesive composite sheet according to claim 6 or 7, The manufacturing method includes a cutting step of using a workpiece group holder in which a plurality of workpieces are aligned and held on the surface of the film-like adhesive in the film-like adhesive composite sheet opposite to the support sheet side, and irradiating the film-like adhesive exposed between the workpieces in the workpiece group holder with laser light to cut the film-like adhesive along the workpieces, thereby producing a workpiece with film-like adhesive, which includes the workpieces and the cut film-like adhesive provided on the workpieces; an energy ray curing step of, after the cutting step, curing the film-like adhesive in the workpiece with the film-like adhesive with energy rays, thereby producing a plurality of workpieces with adhesive-cured material on the support sheet, each workpiece comprising the workpiece and an energy ray-cured product of the film-like adhesive provided on the workpiece; A method for manufacturing a workpiece with a cured adhesive, comprising: a pick-up step of separating the workpiece with the cured adhesive from the support sheet and picking it up after the energy ray curing step.

10. A method for producing a workpiece with a cured adhesive using the film-like adhesive composite sheet according to claim 6 or 7, the gel fraction of the energy ray-cured product of the film-like adhesive in the film-like adhesive composite sheet is 13% or less; The manufacturing method includes an energy ray curing step of using a workpiece group holder in which a plurality of workpieces are aligned and held on a surface of the film-like adhesive in the film-like adhesive composite sheet opposite to the support sheet side, and curing the film-like adhesive in the workpiece group holder with energy rays to produce a hardened workpiece group holder in which a plurality of workpieces are aligned and held on the energy ray-hardened product of the film-like adhesive; a cutting step of, after the energy ray curing step, irradiating a laser beam onto the energy ray-cured material of the film-like adhesive exposed between the workpieces in the cured workpiece group holder to cut the energy ray-cured material along the workpieces, thereby producing a workpiece with an adhesive-cured material, which includes the workpieces and the cut energy ray-cured material provided on the workpieces; A method for manufacturing a workpiece with a cured adhesive, comprising: a pick-up step, after the cutting step, of separating the workpiece with the cured adhesive from the support sheet and picking it up.

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