Film adhesive, film adhesive composite sheet, and method for manufacturing chip with adhesive cured article

Abstract

To provide a film adhesive that achieves a good pickup, from a support sheet, of a chip with an adhesive cured article obtained by carrying out cutting of the energy ray-curable film adhesive by plasma irradiation, and energy ray curing.SOLUTION: A film adhesive 13 is intended for cutting by plasma irradiation. The film adhesive 13 has energy ray curing properties, and a gel fraction of the film adhesive 13 is 22% 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 chip 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. That is, first, 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 surface of the semiconductor wafer (the surface opposite the circuit surface). Next, the semiconductor wafer is divided on the support sheet to produce semiconductor chips, and the film adhesive is cut to produce a plurality of semiconductor chips with the film adhesive on the support sheet. The division of the semiconductor wafer and the cutting of the film adhesive can be carried out successively by blade dicing or the like.

[0004] 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]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-194103 Summary of the Invention [Problem to be solved by the invention]

[0006] On the other hand, dividing the semiconductor wafer and cutting the film adhesive can be carried out successively by plasma irradiation in addition to the blade dicing described above. However, in this case, even though the film adhesive is finally cured by energy rays, it can be difficult to peel the energy ray-cured film adhesive from the support sheet, which can make it difficult to pick up the semiconductor chips with the adhesive cured from the support sheet. In particular, it has been found that if picking up is difficult when the film adhesive is cut by plasma irradiation and then cured with energy rays, picking up is also difficult when the film adhesive is cut by plasma irradiation after being made into an energy ray-cured product.

[0007] So far, we have explained the problems that arise when manufacturing semiconductor chips with cured adhesive from semiconductor wafers in order to manufacture semiconductor devices, but similar problems can also arise when manufacturing chips with cured adhesive from wafers other than semiconductor wafers.

[0008] The present invention aims to provide a film-like adhesive that uses an energy ray-curable film-like adhesive, cut by irradiating it with plasma, and then cured by energy ray, and that enables chips with the cured adhesive to be properly picked up from a support sheet. [Means for solving the problem]

[0009] In order to solve the above problems, the present invention employs the following configuration. [1] A film-like adhesive for cutting by plasma irradiation, the film-like adhesive having energy ray curability and a gel fraction of 22% or less. [2] The film-like adhesive according to [1], wherein the film-like adhesive contains an energy ray-curable component (g) and a photopolymerization initiator (h). [3] The film-like adhesive according to [1] or [2], wherein the energy ray-cured product of the film-like adhesive has a gel fraction of 25% or less. [4] 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-like adhesive according to any one of [1] to [3], wherein the compressive strength is 25 MPa or less. [5] The film adhesive according to any one of [1] to [4], wherein the content of the antioxidant (j1) relative to the total mass of the film adhesive is 0.1 to 5 mass%.

[0010] [6] The film adhesive according to any one of [1] to [5], wherein the content of the polymer component (a) relative to the total mass of the film adhesive is 40 mass % or less. [7] A film-like adhesive composite sheet comprising a support sheet and a film-like adhesive provided on one side of the support sheet, wherein the film-like adhesive is the film-like adhesive described in any one of [1] to [6]. [8] The film-like adhesive composite sheet according to [7], wherein the support sheet consists of only a substrate. [9] Illuminance of 230mW / cm for the film-like adhesive composite sheet 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 The film-like adhesive composite sheet according to [7] or [8], wherein when a peel test is performed in which the support sheet is peeled from the UV-cured product of the film-like adhesive in the test piece (T3), and the support sheet is peeled from the UV-cured product of the 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 product of the film-like adhesive and the support sheet is 100 mN / 25 mm or less.

[0011]

[10] A method for manufacturing a chip with a cured adhesive using the film-like adhesive composite sheet described in any one of [7] to [9], wherein the chip with the cured adhesive comprises a chip and an energy ray-cured product of the film-like adhesive provided on one side of the chip, and the manufacturing method includes attaching the film-like adhesive in the film-like adhesive composite sheet to one side of a wafer, irradiating the wafer and the film-like adhesive with plasma to divide the wafer and produce chips, cutting the film-like adhesive, and curing the film-like adhesive after cutting with energy ray to produce the chip with the cured adhesive, and separating the chip with the cured adhesive from the support sheet and picking it up.

[11] A method for manufacturing a chip with a cured adhesive using the film-like adhesive composite sheet described in any one of [7] to [9], wherein the chip with the cured adhesive comprises a chip and an energy ray-cured product of the film-like adhesive provided on one side of the chip, and the energy ray-cured product of the film-like adhesive has a gel fraction of 25% or less, and the manufacturing method includes attaching the film-like adhesive in the film-like adhesive composite sheet to one side of a wafer, curing the attached film-like adhesive with energy rays to form an energy ray-cured product, irradiating the wafer and the energy ray-cured product with plasma to divide the wafer into chips, cutting the energy ray-cured product to produce the chip with the cured adhesive, and detaching the chip with the cured adhesive from the support sheet and picking it up. [Effects of the Invention]

[0012] According to the present invention, a film-like adhesive is provided which uses an energy ray-curable film-like adhesive, which is cut by irradiation with laser light and then cured with energy rays, and which enables a chip with the cured adhesive to be properly picked up from a support sheet. [Brief explanation of the drawings]

[0013] [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. DETAILED DESCRIPTION OF THE INVENTION

[0014] ◇Film adhesive A film-like adhesive according to one embodiment of the present invention is a film-like adhesive for cutting by plasma irradiation, wherein the film-like adhesive is energy ray curable and has a gel fraction of 22% or less. A chip with an adhesive-cured product, which includes a chip and an energy ray-cured product of the film-like adhesive provided on one side of the chip, is used during the manufacture of a substrate device, as described below. The chip with the adhesive-cured product can be manufactured by irradiating a film-like adhesive-coated wafer, which includes a wafer and the film-like adhesive provided on one side of the wafer, with plasma to divide the wafer on a support sheet, as described below, and cutting the film-like adhesive. The cut film-like adhesive is then energy ray-cured to produce a chip with the adhesive-cured product, which can then be separated from the support sheet and picked up. In this case, since the gel fraction of the unenergy ray-cured film-like adhesive is 22% 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 chip with the adhesive-cured product can be successfully picked up from the support sheet.

[0015] 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.

[0016] In this specification, 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 wafer is a semiconductor wafer, the chips include semiconductor chips. One surface of these wafers is a circuit surface on which circuits are formed, and the opposite surface is referred to as the "back surface" in this specification. The same applies to chips produced by dividing a wafer by means of dicing or the like, and the surface opposite to the circuit surface on which the circuits of the chip are formed is called the "back surface." Both the circuit surface of the wafer and the circuit surface of the chip are provided with protruding electrodes such as bumps and pillars.

[0017] In this specification, the term "substrate device" refers to a device in which a chip with a cured adhesive is adhered to a circuit board by the cured adhesive. For example, if a semiconductor wafer is used as the workpiece, the substrate device may be a semiconductor device.

[0018] 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.

[0019] 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. During the manufacturing process of a substrate device, a chip with a cured adhesive material can be mounted on a circuit board by adhering it to the circuit board using the cured adhesive material. Furthermore, if the cured adhesive material (the 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 material after adhesion has high impact resistance and maintains sufficient adhesive properties even under harsh conditions of high temperature and high humidity.

[0020] In this specification, the term "energy ray" refers to an electromagnetic wave or a charged particle beam that has an energy quantum. Examples of energy rays include ultraviolet rays, radioactive rays, and electron beams. 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.

[0021] 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.

[0022] The energy ray-curable film-like adhesive of the present embodiment preferably contains an energy ray-curable component (g), and more preferably contains an energy ray-curable component (g) and a photopolymerization initiator (h). The film adhesive of this embodiment preferably contains a polymer component (a) because it has good film-forming properties. The film adhesive of this embodiment preferably contains an antioxidant (j1) in order to improve the pick-up properties of the chip with the cured adhesive attached thereto. The components contained in the film-like adhesive of this embodiment will be described in detail later.

[0023] In this specification, the property of being able to normally pick up an object, such as a chip with a cured adhesive attached thereto, from a support sheet by separating it from the support sheet is sometimes referred to as "pick-up ability."

[0024] <Gel fraction of film adhesive> The gel fraction of the film-like adhesive is 22% or less. In contrast, when chips with cured adhesive are manufactured using a film-like adhesive composite sheet configured with a conventional film-like adhesive having a gel fraction exceeding 22%, unlike the present embodiment, the chips with 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.

[0025] That is, when a conventional film-like adhesive composite sheet, which is a laminate of a conventional film-like adhesive and a support sheet, is irradiated with plasma to cut the film-like adhesive, it is presumed that the cut film-like adhesive or its modified product and the support sheet or its modified product become intricately entangled and interact with each other, restricting their free movement. In this specification, this phenomenon is referred to as "anchoring." It is presumed that this may prevent the chip with the cured adhesive from being picked up from the support sheet even if the film-like adhesive is cured with energy rays. In this way, if the pickup ability of a chip with a cured adhesive becomes poor when a film-like adhesive is irradiated with plasma, a similar problem usually occurs when an energy ray-cured product of the film-like adhesive (cured adhesive product) is irradiated with plasma and the cured adhesive product is cut. In contrast, these problems are resolved by using the film adhesive of the present embodiment, presumably because anchoring between the energy ray-cured product of the film adhesive (cured adhesive product) and the support sheet or a modified product thereof is suppressed.

[0026] In order to obtain the above-mentioned effects of the present invention more significantly, the lower the gel fraction of the film adhesive, the better, and it may be, for example, any one of 18% or less, 14% or less, 10% or less, and 7% or less. On the other hand, a film adhesive with a gel fraction of 0.5% or more can be more easily achieved.

[0027] When the film adhesive contains a filler (d) described below, the gel fraction of the film adhesive refers to the gel fraction of the components of the film adhesive other than the filler (d). This is because the filler (d) does not contribute to gelation. The gel fraction of the film adhesive refers to the degree of gelation when the components in the film adhesive gel.

[0028] 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. 11The 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)

[0029] 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.

[0030] <Gel fraction of energy ray cured film adhesive> The gel fraction of the energy ray-cured film adhesive (cured adhesive product) is preferably 25% 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 lower, and the use of such a film adhesive improves the pick-up ability of the chip with the cured adhesive product. Furthermore, by using such a film-like adhesive, not only the chip with the cured adhesive obtained by cutting the film-like adhesive attached to the chip by irradiating it with plasma and then curing it with energy rays, but also the chip with the cured adhesive obtained by curing the film-like adhesive attached to the chip by energy rays and then cutting the energy ray-cured film-like adhesive by irradiating it with plasma have improved pick-up properties.

[0031] 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.

[0032] 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.

[0033] 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. 21The 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 adhesive, the gel fraction of the energy ray-cured film 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)

[0034] 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.

[0035] <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 25 MPa or less, more preferably 1.4 MPa or less, and may be, for example, 0.3 MPa or less. 23When ' is equal to or less than the upper limit, the pick-up properties of the chip with the cured adhesive are 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 tensile strength of 0.04 MPa or more can be achieved more easily.

[0036] 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.

[0037] 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.

[0038] <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 curing the laminate with energy rays. 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 23The G of the energy ray-cured product of the film-like adhesive is preferably 70 MPa or less, more preferably 66 MPa or less, and even more preferably 62 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 chip with the cured adhesive. Furthermore, the use of such a film-like adhesive improves the adhesion when the chip 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.

[0039] 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).

[0040] 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 '.

[0041] <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.

[0042] 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 in the form of a roll, for example.

[0043] The film adhesive 13 is intended to be cut by plasma irradiation and has energy ray curing properties. The gel fraction of the film adhesive 13 is 22% or less.

[0044] The first release film 151 and the second release film 152 may both be known films. 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.

[0045] One of the first surface 13a and the second surface 13b of the film adhesive 13 is the surface to be attached to one surface of the wafer, and the other is the surface to be attached to the support sheet described below.

[0046] <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.

[0047] 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."

[0048] 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, the "thickness of the film adhesive" refers to the thickness of the entire film adhesive, and for example, the thickness of a film adhesive consisting of multiple layers refers to the total thickness of all layers that make up the film adhesive. This also applies to other layers such as the substrate, pressure-sensitive adhesive layer, and intermediate release layer, which will be described later.

[0049] 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.

[0050] <<Adhesive composition>> The film-like adhesive can be formed using an adhesive composition containing the constituent materials thereof. For example, the film-like adhesive can be formed at the desired site by applying the adhesive composition to the surface on which the film-like adhesive is to be formed by a known method and drying it as necessary. 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.

[0051] In this specification, "room temperature" means a temperature that is neither particularly cold nor hot, that is, a normal temperature, and examples thereof include temperatures of 18 to 28°C.

[0052] 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 %.

[0053] 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.

[0054] 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).

[0055] The polymer component (a), energy ray-curable component (g), photopolymerization initiator (h), thermosetting component (b), and curing accelerator (c) contained in the composition (III) and the film-like adhesive may each 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.

[0056] <Polymer component (a)> The polymer component (a) is a component that can be considered to be formed by a polymerization reaction of a polymerizable compound, and is a polymer compound that imparts film-forming properties, flexibility, etc. to the film-like adhesive. In this specification, the polymer compound also includes products of polycondensation reactions.

[0057] Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, saturated polyester resins, etc., with acrylic resins being preferred.

[0058] 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.

[0059] In this specification, unless otherwise specified, the "weight average molecular weight" is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0060] 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 chip with the cured adhesive from the support sheet, which will be described later. 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 chip is improved.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] Examples of the (meth)acrylic acid ester constituting the acrylic resin include (meth)acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a chain structure containing 1 to 18 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; (meth)acrylic acid cycloalkyl esters such as dicyclopentanyl (meth)acrylate; glycidyl group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate; and hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate.

[0065] 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.

[0066] 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 be bonded to other compounds via a crosslinking agent (f) described below, or may be bonded directly to other compounds without the crosslinking agent (f).

[0067] 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 40 mass% or less, regardless of the type of polymer component (a), and may be, for example, either 30 mass% or less or 23 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 plasma, 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.

[0068] 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 equivalent to saying that 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 40 mass% or less, regardless of the type of polymer component (a), and may be, for example, either 30 mass% or less or 23 mass% or less, while the proportion is preferably greater than 0 mass% and 8 mass% or more. 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.

[0069] <Energy ray curable component (g)> The energy ray-curable component (g) makes it easy to apply the film-like adhesive to a wafer at normal temperature (for example, room temperature), and also makes it easy to pick up the chip with the cured adhesive from the support sheet. 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.

[0070] 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.

[0071] 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.

[0072] The molecular weight or weight average molecular weight of the energy ray-curable component (g) is preferably 100 to 30,000, and more preferably 300 to 10,000.

[0073] 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, and may be, for example, 7 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 rays. 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).

[0074] <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.

[0075] 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.

[0076] 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 even more preferably 1 to 6 parts by mass, per 100 parts by mass of the energy ray-curable component (g).

[0077] <Thermosetting component (b)> The thermosetting component (b) has thermosetting properties and is a component for thermally curing the film-like adhesive. 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.

[0078] [Epoxy thermosetting resin] The epoxy thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b2). The epoxy resin (b1) and the thermosetting agent (b2) contained in the composition (III) and the film-like adhesive may each be a single type or two or more types, and when two or more types are contained, the combination and ratio thereof can be selected arbitrarily.

[0079] (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.

[0080] 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.

[0081] 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 chip with the cured adhesive is improved.

[0082] 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, 5 to 12 times by mass, or 7 to 12 times by mass, or 3 to 10 times by mass, or 3 to 8 times by mass, or may be 5 to 10 times by mass.

[0083] 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. On the other hand, when this ratio is equal to or less than 100% by mass.

[0084] (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.

[0085] 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).

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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, 200 to 1,000 parts by mass, 300 to 1,000 parts by mass, or 200 to 800 parts by mass. Having the content of the thermosetting component (b) within this range makes it easier to adjust the adhesive strength between the film-like adhesive and the support sheet described below.

[0090] <Curing accelerator (c)> The curing accelerator (c) is a component for adjusting the thermal curing rate of the film adhesive. Preferred examples of the curing accelerator (c) include 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; tertiary amines; organic phosphines (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylboron salts; and clathrate compounds in which the imidazoles are used as guest compounds.

[0091] 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.

[0092] 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.

[0093] <Filling material (d)> By using a film adhesive containing the filler (d), it is possible to reduce the moisture absorption rate of the cured product and improve the heat dissipation properties, and furthermore, it is possible to improve the reliability of the package. The average particle size of the filler (d) is not particularly limited, but is preferably 10 nm to 5 μm.

[0094] 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.

[0095] 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.

[0096] In the film-like adhesive, the content of filler (d) relative to the total mass of the film-like adhesive is preferably less than 15 mass%, more preferably 10 mass% or less, even more preferably 5 mass% or less, and particularly preferably 3 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 plasma, 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).

[0097] <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.

[0098] The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (a), the thermosetting component (b), etc., and is more preferably a silane coupling agent.

[0099] 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.

[0100] 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.

[0101] <Crosslinking agent (f)> When the polymer component (a) has functional groups such as vinyl groups, (meth)acryloyl groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can bond with other compounds, such as the above-mentioned acrylic resins, the crosslinking agent (f) crosslinks the functional groups in the polymer component (a) by bonding them with other compounds, thereby adjusting the initial adhesive strength and cohesive strength of the film-like adhesive.

[0102] 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).

[0103] In the composition (III) and the film-like adhesive, the content of the crosslinking agent (f) is preferably 6 parts by mass or less, and more preferably 3 parts by mass or less, per 100 parts by mass of the content of the polymer component (a). On the other hand, the content is 0 parts by mass or more. Since the lower the content of crosslinking agent (f), the higher the pick-up ability of the chip with the cured adhesive tends to be, it is particularly preferable that the content is 0 parts by mass, i.e., the film-like adhesive does not contain crosslinking agent (f).

[0104] <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.

[0105] 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.

[0106] <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. In particular, the use of a film adhesive containing an antioxidant (sometimes referred to herein as "antioxidant (j1)") improves the pick-up properties of chips with a cured adhesive. This is presumably because, when the film adhesive or its energy ray-cured product (cured adhesive product) is irradiated with plasma, unnecessary radicals are captured in the film adhesive or its energy ray-cured product (cured adhesive product), ultimately resulting in a desirable composition of the cured adhesive product. That is, a preferred general-purpose additive (j) contained in the composition (III) and the film-like adhesive is an antioxidant (j1).

[0107] Examples of the antioxidant (j1) include hindered amine light stabilizers. Examples of the hindered amine light stabilizer include p,p'-dioctyldiphenylamine, phenyl-α-naphthylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N,N'-diphenyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diallyl-p-phenylenediamine, and 4,4'-(α,α-dimethylbenzyl)diphenylamine. , p,p-toluenesulfonylaminodiphenylamine, N-phenyl-N'-(3-methacloryloxy-2-hydroxypropyl)-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine, alkylated diphenylamines, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[[6-( 1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,Mixed esters of 4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5 Examples of suitable esters include a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, (2,2,6,6-tetramethylene-4-piperidyl)-2-propylenecarboxylate, and (1,2,2,6,6-pentamethyl-4-piperidyl)-2-propylenecarboxylate.

[0108] Among these, the hindered amine light stabilizer is preferably a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, which is an N-alkyl hindered amine light stabilizer.

[0109] 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).

[0110] When the composition (III) and the film adhesive contain an antioxidant (j1), the content of the antioxidant (j1) in the film adhesive relative to the total mass of the film adhesive is preferably 0.05 to 15 mass%, and may be, for example, 0.1 to 10 mass%, or 0.5 to 5 mass%. When this proportion is equal to or greater than the lower limit, the pick-up ability of the chip with the cured adhesive is improved. When this proportion is equal to or less than the upper limit, excessive use of the antioxidant (j1) is suppressed.

[0111] When the composition (III) and the film adhesive contain a general-purpose additive (i) other than the antioxidant (j1), the content of the general-purpose additive (i) other than the antioxidant (j1) in the film adhesive may be, for example, 0.1 to 10 mass % relative to the total mass of the film adhesive.

[0112] <Solvent> Composition (III) preferably further contains a solvent, which improves the handleability of composition (III). 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.

[0113] The solvent is not particularly limited, but preferred examples include hydrocarbons such as toluene; alcohols such as methanol; 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.

[0114] 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.

[0115] <<Example of film adhesive>> An example of a preferred film-like adhesive of this embodiment is a film-like adhesive for cutting by plasma irradiation, the film-like adhesive is energy ray-curable, the film-like adhesive has a gel fraction of 22% 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 40 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, the film-like adhesive does not contain a filler (d), or, if the film-like adhesive further contains a filler (d), the content of the filler (d) in the film-like adhesive relative to the total mass of the film-like adhesive is more than 0 mass% and less than 15 mass%, The film-like adhesive may not contain an antioxidant (j1), or may further contain an antioxidant (j1), and when the film-like adhesive contains the antioxidant (j1), the content of the antioxidant (j1) relative to the total mass of the film-like adhesive may be 0.05 to 15 mass%. Such a film-like adhesive further contains a thermosetting component (b) and a curing accelerator (c), and it is more preferable that the content of the thermosetting component (b) in the film-like adhesive is 20 to 1000 parts by mass per 100 parts by mass of the content of the polymer component (a).

[0116] <<Method of manufacturing adhesive composition>> The adhesive composition (for example, composition (III)) can be obtained by blending the components that constitute it. 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.

[0117] ◇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 wafer by irradiating it with plasma. In either case, as will be described later, the chips with the cured adhesive obtained after the plasma irradiation are finally separated from the support sheet and picked up. In the film-like adhesive composite sheet of this embodiment, the gel fraction of the film-like adhesive is 22% or less, so that the chip with the cured adhesive can be picked up normally from the support sheet without difficulty and has high pick-up properties.

[0118] The film-like adhesive composite sheet of this embodiment may be the same as a conventional film-like adhesive composite sheet, except that it comprises the film-like adhesive of this embodiment described above.

[0119] <<Support sheet>> 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.

[0120] 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 film-like adhesive composite sheet has the adhesive layer and intermediate release layer arranged in this order between the substrate and the film-like adhesive, from the substrate side to the film-like adhesive side. The adhesive layer and intermediate release layer are layers that make it easier to pick up the chip with the cured adhesive, which will be described later, from the support sheet.

[0121] Since the film adhesive has energy ray curing properties, the support sheet is preferably made of only a substrate, which allows the structure of the support sheet to be simplified.

[0122] The substrate, adhesive layer, and intermediate release layer may each consist of one layer (single layer), or may consist of two or more layers. When consisting 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.

[0123] FIG. 2 is a cross-sectional view schematically showing an example of the film-like adhesive composite sheet of this embodiment. 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] When the film-like adhesive composite sheet 101 is used, with the release film 15 removed, a wafer 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.

[0128] The film-like adhesive composite sheet of this embodiment is not limited to that shown in Figure 2, and for example, some of the components of this film-like adhesive composite sheet may be changed, deleted, or added within the scope of the present invention.

[0129] For example, the support sheet 10 may be constructed by laminating a substrate 11 and an adhesive layer in this order in the thickness direction toward the film-like adhesive 13 side, or may be constructed by laminating a substrate 11, an adhesive layer, and an intermediate release layer in this order in the thickness direction.

[0130] The film-like adhesive composite sheet of this embodiment has a pressure-sensitive adhesive layer, and if a portion of the surface of the pressure-sensitive adhesive layer opposite the substrate side is exposed, it does not need to have a jig adhesive layer.

[0131] Next, each layer constituting the film-like adhesive composite sheet of this embodiment will be described in more detail.

[0132] <Base material> The substrate may be in the form of a sheet or film, and may be any known substrate. The substrate is preferably one that transmits energy rays. Examples of materials that can be used for the substrate include various resins. 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.

[0133] 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. The resin may be any of a polymer alloy such as a mixture of two or more of the above-mentioned resins, a crosslinked resin in which one or more of the above-mentioned resins are crosslinked, and a modified resin such as an ionomer using one or more of the above-mentioned resins.

[0134] 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).

[0135] The thickness of the substrate is preferably 50 to 300 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 wafer are improved.

[0136] The surface of the substrate may or may not be subjected to an oxidation treatment, an oleophilic treatment, a hydrophilic treatment, a primer treatment, or the like, and may or may not have another layer vapor-deposited thereon.

[0137] 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.

[0138] <Adhesive layer> The pressure-sensitive adhesive layer is in the form of a sheet or film and contains a pressure-sensitive adhesive. 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. The pressure-sensitive adhesive layer is preferably one that transmits energy rays.

[0139] The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm.

[0140] The pressure-sensitive adhesive layer may be either energy ray curable or non-energy ray curable. When the adhesive layer is energy ray curable, the chip with the cured adhesive material can be picked up more easily by curing the adhesive layer with energy rays and then picking it up from the support sheet. In this embodiment, the support sheet after the pressure-sensitive adhesive layer has been cured by energy rays is also simply referred to as the support sheet, as long as the other laminated structures are maintained.

[0141] 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 site. 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.

[0142] <Intermediate release layer> The intermediate release layer is in the form of a sheet or film, and may be any known material. 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. The intermediate release layer is preferably one that transmits energy rays.

[0143] The resin layer in the intermediate release layer provided with a release treatment layer and the intermediate release layer consisting of a single resin layer can both be produced by molding a resin composition containing a resin. The intermediate release layer having a release-treated layer can be produced by subjecting one surface of the resin layer to release treatment.

[0144] The release treatment 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.

[0145] 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 that is the constituent material of the intermediate release layer consisting of a single resin layer include ethylene-vinyl acetate copolymer.

[0146] 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. When the thickness of the intermediate release layer is equal to or less than the upper limit, the force pushing up from the support sheet side is more easily transmitted to the chip with the cured adhesive when the chip with the cured adhesive is picked up, making the pick-up easier.

[0147] <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.

[0148] <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.

[0149] <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, or a jig adhesive layer. The other layers can be arbitrarily selected depending on the purpose and are not particularly limited.

[0150] The film-like adhesive composite sheet of this embodiment preferably does not include the other layer between the support sheet and the film-like adhesive. Use of such a film-like adhesive composite sheet improves the pick-up ability of chips with the cured adhesive.

[0151] <<Peel strength between the energy ray cured film adhesive and the support sheet>> When using the film-like adhesive composite sheet of this embodiment, the degree of pick-up ability of a chip with a cured adhesive product 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 indicator.

[0152] 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 2A 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) curing the film-like adhesive with energy rays. 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 its length direction at a peel rate of 300 mm / min, with the angle between the surface of the energy ray-cured product to which the support sheet was attached being 180° and the surface of the support sheet to which 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 chips with cured adhesive.

[0153] 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 Figure 2, and the test piece (T3) may have or may not have a release film.

[0154] 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), for example, by 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.

[0155] 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.

[0156] The peel strength between the energy ray-cured film adhesive and the support sheet is more preferably 70 mN / 25 mm or less, and even more preferably 40 mN / 25 mm or less. On the other hand, in terms of being highly effective in preventing the chip with the cured adhesive from unintended peeling from the support sheet, the peel force is preferably 10 mN / 25 mm or more.

[0157] 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.

[0158] ◇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 so that they are in a corresponding positional relationship, and adjusting the shapes of some or all of the layers as necessary. The method for forming each layer is as described above. The film-like adhesive composite sheet of this embodiment can be produced in the same manner as conventional film-like adhesive composite sheets, except that the film-like adhesive is used.

[0159] For example, when laminating a film-like adhesive onto a support sheet, the adhesive composition is applied to a release film and dried as necessary to form a film-like adhesive on the release film, and the exposed surface of this film-like adhesive is then bonded to one side of the support sheet. When manufacturing a support sheet having a laminated structure of a substrate and an adhesive layer, for example, an adhesive composition is applied to a release film and dried as necessary to form an adhesive layer on the release film, and the exposed surface of this adhesive layer is then bonded to one surface of the substrate. When laminating an intermediate release layer onto a substrate, the intermediate release layer is prepared in advance using the same method as for the adhesive layer, and then laminated to the desired lamination location (e.g., the adhesive layer).

[0160] ◇Manufacturing method for chips with cured adhesive (method for using film-like adhesive composite sheet) The film-like adhesive composite sheet can be used to manufacture a chip with a cured adhesive, and the obtained chip with a cured adhesive can further be used to manufacture a substrate device. By using the film-like adhesive composite sheet, when manufacturing a chip with a cured adhesive, the film-like adhesive is cut by irradiating with plasma and then cured with energy rays, and the chip 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 25% or less, even if the film-like adhesive is cured into an adhesive by energy ray curing and then cut by irradiating with plasma, the chip with the cured adhesive can be properly picked up from the support sheet, thereby expanding the options for manufacturing semiconductor chips with a cured adhesive.

[0161] <<Manufacturing method (1)>> A method for producing a chip with a cured adhesive according to one embodiment of the present invention is a method for producing a chip with a cured adhesive using the film-like adhesive composite sheet according to one embodiment of the present invention described above, In the manufacturing method, the film adhesive in the film adhesive composite sheet is attached to one side of a wafer, and the wafer and film adhesive are irradiated with plasma to divide the wafer into chips. The film adhesive is then cut, and the cut film adhesive is cured with energy rays to produce a chip with the cured adhesive, which is then separated from the support sheet and picked up (in this specification, this manufacturing method is sometimes referred to as "manufacturing method (1)").

[0162] The manufacturing method (1) may be the same as the conventional manufacturing method of a chip with a cured adhesive, except that the film-like adhesive composite sheet of this embodiment described above is used instead of the conventional film-like adhesive composite sheet.

[0163] In the production method (1), the film-like adhesive composite sheet can be attached to the wafer by a known method, and is preferably attached at normal temperature (for example, room temperature).

[0164] In the production method (1), preferred gases used to generate plasma during plasma irradiation include, for example, oxygen (O2) gas, sulfur hexafluoride (SF6) gas, and tetrafluoromethane (CF4) gas. The flow rate of the gas that generates the plasma is preferably 50 to 300 cc. The output during plasma irradiation is preferably 200 to 400W.

[0165] In the production method (1), the energy ray irradiation conditions (illuminance, amount of light) when the film adhesive is cured with energy ray are as described above.

[0166] In manufacturing method (1), the chip with the cured adhesive can be picked up by a known method. When the support sheet consists of only a substrate, the chip with the cured adhesive is peeled off from the substrate at the time of pickup. When the support sheet has a pressure-sensitive adhesive layer as the outermost layer, the chip with the cured adhesive is peeled off, for example, from the pressure-sensitive adhesive layer or its energy ray-cured product. When the support sheet has an intermediate release layer as the outermost layer, the chip with the cured adhesive is peeled off from the intermediate release layer. Regardless of the support sheet, the chip with the cured adhesive is highly pickable.

[0167] <<Manufacturing method (2)>> A method for producing a chip with a cured adhesive according to one embodiment of the present invention is a method for producing a chip with a cured adhesive using the film-like adhesive composite sheet according to one embodiment of the present invention described above, the energy ray-cured product of the film-like adhesive has a gel fraction of 25% or less, In the manufacturing method, the film adhesive in the film adhesive composite sheet is attached to one side of a wafer, the attached film adhesive is cured with energy rays to form an energy ray-cured product, the wafer and the energy ray-cured product are irradiated with plasma to divide the wafer into chips, and the energy ray-cured product is cut to produce chips with the adhesive-cured product, which are then detached from the support sheet and picked up (in this specification, this manufacturing method may be referred to as "manufacturing method (2)").

[0168] Manufacturing method (2) is the same as manufacturing method (1), except that the film-like adhesive composite sheet of the present embodiment described above uses a film-like adhesive whose energy ray-cured product has a gel fraction of 25% or less, and the order of plasma irradiation and energy ray irradiation is reversed.

[0169] In the manufacturing method (2), the film-like adhesive composite sheet can be attached to the wafer in the same manner as in the manufacturing method (1).

[0170] The energy ray irradiation conditions and plasma irradiation conditions in the production method (2) are the same as the energy ray irradiation conditions and plasma irradiation conditions in the production method (1), respectively.

[0171] In manufacturing method (2), the chip with the cured adhesive can be picked up in the same manner as in manufacturing method (1). The chip with the cured adhesive is then peeled off from the support sheet in the same manner as in manufacturing method (1). Regardless of the support sheet, the chip with the cured adhesive is highly pickable, just like in manufacturing method (1).

[0172] <<Modification of the manufacturing method of the chip with cured adhesive>> In the manufacturing method of the chip with the cured adhesive of this embodiment (manufacturing method (1) and manufacturing method (2)), other steps that do not fall under the above-mentioned steps (attaching the film-like adhesive composite sheet to the wafer, irradiating the wafer and the film-like adhesive with plasma, or irradiating the wafer and the energy ray-cured film-like adhesive with plasma, irradiating the film-like adhesive with energy rays before or after cutting, and picking up the chip with the cured adhesive) may or may not be performed, as long as the effects of the present invention are not impaired. The types and timing of the other steps can be arbitrarily selected depending on the purpose, and further can be arbitrarily selected depending on the type of film-like adhesive composite sheet or wafer, and are not particularly limited.

[0173] In the manufacturing method of this embodiment, the wafer is divided and the film-like adhesive or its energy ray-cured product is cut consecutively by irradiating plasma on the support sheet. However, the wafer may be divided in advance and only the film-like adhesive or its energy ray-cured product is cut by irradiating plasma. In this case, instead of the wafer with the film-like adhesive composite sheet, a chip group holder is used in which multiple chips are aligned and held on the surface of the film-like adhesive in the film-like adhesive composite sheet opposite the support sheet. The wafer is not divided, and only the film-like adhesive or its energy ray-cured product is cut. The remaining steps are the same as in manufacturing method (1) or (2) described above, thereby producing chips with the adhesive-cured product. The chip group holder can be produced by a known method.

[0174] ◇ Manufacturing method of substrate device (method of using chip with cured adhesive) A substrate device can be manufactured using the chip with the cured adhesive obtained by the above manufacturing method. The substrate device can be manufactured by a known method, except for using the above-mentioned chip with the cured adhesive. For example, the chip with the cured adhesive is bonded to a circuit board using the cured adhesive (energy ray cured film adhesive) contained therein, and if the film adhesive is thermosetting, the energy ray cured film adhesive after mounting is further thermally cured. Furthermore, by performing other processes as necessary, the desired substrate device can be manufactured. [Example]

[0175] 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.

[0176] <<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

[0177] <<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: Acrylic resin ("Teisan Resin (registered trademark) SG-P3" manufactured by Nagase ChemteX Corporation) [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) [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) [Curing accelerator (c)] (c)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezol (registered trademark) 2PHZ-PW" manufactured by Shikoku Chemicals Corporation) [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) [Antioxidants (j1)] (j1)-1: Mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (hindered amine light stabilizer, "ADEKA STAB (registered trademark) LA-63P" manufactured by ADEKA Corporation)

[0178] [Example 1] <<Manufacturing of film adhesives>> <Production of Adhesive Composition> Each component was dissolved or dispersed in methyl ethyl ketone so that the type and content of the components in the film-like adhesive were as 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%.

[0179] <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, by bonding the release-treated surface of a separate release film (first release film, "SP-PET381031" manufactured by Lintec Corporation, thickness 38 μm) to the exposed surface of the obtained film adhesive (film adhesive (F1)) that did not have the second release film, a film adhesive with a release film was produced, 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.

[0180] <<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 a measurement sample was prepared using the method described above, using staples as fasteners. 11 , M2 and M3 were weighed. M4 was 0. Next, the measurement sample is immersed, taken out, dried and conditioned by the method described above, and the M in the formula (i) is measured using a precision balance. 51 The gel fraction of the film-like adhesive was then calculated using the above formula (i). The results are shown in Table 1 in the column "Gel fraction (%) of film-like adhesive."

[0181] <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, a measurement sample was prepared using the UV-cured film adhesive obtained in this way, using staples as fasteners, in the manner described above. 21 , M2 and M3 were weighed. M4 was 0. Next, the measurement sample is immersed, taken out, dried and conditioned by the method described above, and the M in formula (ii) is measured using a precision balance. 52 The gel fraction of the UV-cured film-like adhesive was then calculated using formula (ii) above. The results are shown in Table 1 in the column "Gel fraction (%) of energy ray-cured film-like adhesive."

[0182] <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 23The results are shown in Table 1.

[0183] <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.

[0184] <<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.

[0185] <<Manufacturing silicon chips with cured adhesive>> A silicon chip with a cured adhesive was manufactured by manufacturing method (1) according to the following procedure.

[0186] <Preparation of Silicon Chip Group Holder> Using a half-cut dicer (DISCO Corporation, "DFG6363"), half-cuts were made to form grooves at intervals 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). This left a thickness of 50 μm in the areas of the silicon wafer where no grooves were formed, and grooves appeared on the ground surface of the silicon wafer. The silicon wafer was then divided at the grooves to produce silicon chips (0.5 mm x 0.5 mm).

[0187] 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 (silicon chip group) obtained above at room temperature. 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.

[0188] The reason why the silicon wafer was divided before the evaluation was that it had been confirmed that even when the silicon wafer was divided into a group of silicon chips and these silicon chips and a film-like adhesive composite sheet were used for evaluation, the same evaluation results as when an undivided silicon wafer and a film-like adhesive composite sheet were used for evaluation were obtained, and the use of silicon chips and a film-like adhesive composite sheet made evaluation easier and more accurate, and this also applies to the other examples and comparative examples described below.

[0189] <Preparation of silicon chips with film adhesive> Using the silicon chip group holder obtained above, the film-like adhesive exposed between the silicon chips was irradiated with plasma, thereby cutting the film-like adhesive along the silicon chips. More specifically, a Yamato Scientific Plasma Dry Cleaner "PDC210" was used as the apparatus. The silicon chip group holder was stored in the apparatus, and the film-like adhesive was irradiated with plasma for 1 minute under conditions of O2 gas, flow rate of 100 cc, and output of 300 W. The silicon chip group holder was then removed from the apparatus and allowed to cool in an air atmosphere, and the atmosphere inside the apparatus was replaced with air. Next, under the same conditions as above, the film-like adhesive in the silicon chip group holder was irradiated with plasma again within the apparatus. The silicon chip group holder was then removed from the apparatus and allowed to cool in an air atmosphere, and the atmosphere inside the apparatus was replaced with air. Furthermore, the film adhesive was irradiated with plasma and the silicon chip group holder was allowed to cool 13 times (for a total of 15 times), and the film adhesive was irradiated with plasma for a total of 15 minutes, cutting the film adhesive exposed between the silicon chips. In this way, the film adhesive was irradiated with plasma while the silicon chip group holder was allowed to cool in order to prevent excessive temperature rise in the film adhesive due to plasma irradiation. In this way, a silicon chip with a film adhesive was produced, which included a silicon chip and a cut piece of film adhesive provided on the back surface of the silicon chip. These multiple silicon chips with a film adhesive were aligned and held on the support sheet (s1), and together with the support sheet (s1), constituted a group of silicon chips with a film adhesive.

[0190] <Preparation of silicon chips with cured adhesive> The film adhesive in the group of silicon chips with film adhesive obtained above was irradiated with an ultraviolet ray irradiation device ("RAD2010m / 12" manufactured by Lintec Corporation) equipped with a high-pressure mercury lamp under a nitrogen gas atmosphere at an illuminance of 220 mW / cm. 2 , light intensity 190mJ / cm 2 The film-like adhesive was UV-cured by irradiating it with UV rays under the conditions. In this way, a plurality of silicon chips with cured adhesive were produced on the support sheet (s1), each comprising a silicon chip and a UV-cured film-like adhesive provided on the back surface of the silicon chip. These plurality of silicon chips with cured adhesive were aligned and held on the support sheet (s1), and together with the support sheet (s1), constituted a group of silicon chips with cured adhesive. The group of silicon chips with cured adhesive had a substantially circular shape when viewed in plan.

[0191] (Manufacturing silicon chips with cured adhesive) Using a pickup and die bonding machine (Canon Machinery's "BESTEM D-510"), we attempted 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 this experiment, we viewed the group of silicon chips with cured adhesive from a plan view, and determined a center and two line segments that intersected each other at the center and extended to just before the periphery of the group of silicon chips with cured adhesive. Two locations were selected from the center or its vicinity, and two locations were selected from each end of the line segments (a total of eight locations). A total of ten locations were selected in the group of silicon chips with cured adhesive. Ten silicon chips with cured adhesive were picked up one by one from each location. The pin thrust speed was 5 mm / s, and the pin thrust height was 200 μm. Five pins were used to thrust up one silicon chip with cured adhesive from the support sheet (s1).

[0192] <<Evaluation of film adhesive composite sheets>> <Evaluation of pick-up ability of silicon chips with cured adhesive> After the above pick-up, the pick-up ability of the silicon chip with the cured adhesive was evaluated according to the following criteria. The results are shown in the "Pick-up ability" column in Table 1. [Evaluation criteria] A: 10 silicon chips with cured adhesive were successfully picked up. B: Nine silicon chips with cured adhesive were successfully picked up. C: 6 to 8 silicon chips with cured adhesive were successfully picked up. D: Five or more silicon chips with cured adhesive could not be picked up normally.

[0193] <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 220 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 section was cured by ultraviolet light, and a test piece (T3) with a release film was prepared.

[0194] 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). Then, the exposed surface of the UV-cured film adhesive in the test piece (T3) was 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.

[0195] 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 peel rate 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° and the surface of the support sheet (s1) to which the UV-cured film-like adhesive 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.

[0196] <<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 6] Except for changing the amounts of the components of the adhesive composition, film-like adhesives were produced in the same manner as in Example 1. The types and amounts of the components contained in these film-like adhesives are shown in Tables 1 and 2. In addition, the notation "-" in the column for the component contained in the film adhesive means that the film adhesive does not contain that component.

[0197] Furthermore, film-like adhesive composite sheets were produced in the same manner as in Example 1, except that these film-like adhesives were used. These film adhesives and film adhesive composite sheets were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. Hereinafter, in this specification, the film adhesive obtained in Example 2 will be referred to as "film adhesive (F2)", and film adhesives obtained in other Examples may also be similarly referred to by the number of the Example.

[0198] [Example 7] Using the film-like adhesive composite sheet obtained in Example 1, silicon chips with cured adhesive were manufactured by manufacturing method (2) by changing the timing of ultraviolet irradiation from after plasma irradiation to before plasma irradiation (switching the order of ultraviolet irradiation and plasma irradiation), unlike in Example 1, during the production of the above-mentioned group of silicon chips with cured adhesive. More specifically, this is as follows.

[0199] <<Manufacturing silicon chips with cured adhesive>> <Preparation of Silicon Chip Group Holder> A silicon chip group holder was produced in the same manner as in Example 1.

[0200] <Preparation of silicon chips with film adhesive> The film adhesive (film adhesive (F1)) in the silicon chip group holder obtained above was irradiated with ultraviolet light under the same conditions as in Example 1, thereby curing the film adhesive. In this way, a cured silicon chip group holder was produced in which a plurality of silicon chips were aligned and held on the UV-cured film adhesive.

[0201] <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 plasma 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 film on the back surface of the silicon chip. 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. The silicon chip group with the cured adhesive had a roughly circular shape when viewed in plan.

[0202] <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.

[0203] <<Evaluation of film adhesive composite sheets>> <Evaluation of pick-up ability of silicon chips with cured adhesive> After picking up the silicon chip with the cured adhesive as described above, the pick-up ability of the silicon chip with the cured adhesive was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0204] In all the tables shown below, including Table 2, the timing of ultraviolet irradiation during the production of the silicon chip with cured adhesive, whether it was before or after plasma irradiation, is indicated by the symbol "*".

[0205] <<Production of silicon chips with cured adhesive and evaluation of film-like adhesive composite sheets>> [Example 8] Using the film-like adhesive composite sheet obtained in Example 3, unlike in Example 3, the timing of ultraviolet irradiation was changed from after plasma irradiation to before plasma irradiation (the order of ultraviolet irradiation and plasma irradiation was reversed) during the preparation of the silicon chip group with the cured adhesive, and silicon chips with the cured adhesive were produced. In other words, silicon chips with the cured adhesive were produced in the same manner as in Example 7, except that the film-like adhesive composite sheet obtained in Example 3 was used instead of the film-like adhesive composite sheet obtained in Example 7. The film-like adhesive composite sheet was then evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0206] [Example 9] Using the film-like adhesive composite sheet obtained in Example 4, unlike in Example 4, the timing of ultraviolet irradiation was changed from after plasma irradiation to before plasma irradiation (the order of ultraviolet irradiation and plasma irradiation was reversed) during the production of the silicon chip group with the cured adhesive, and silicon chips with the cured adhesive were produced. The film-like adhesive composite sheet was then evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0207] <<Production and evaluation of film-type adhesives, production of silicon chips with cured adhesives, and production and evaluation of film-type adhesive composite sheets>> [Comparative Example 1] Except for changing the amounts of the components of the adhesive composition, a film-like adhesive was produced in the same manner as in Example 1. The types and amounts of the components contained in this film-like adhesive are shown in Table 3. Furthermore, a film-like adhesive composite sheet was produced in the same manner as in Example 1, except that this film-like adhesive was used. These film adhesives and film adhesive composite sheets were evaluated in the same manner as in Example 1. The results are shown in Table 3. Hereinafter, in this specification, the film adhesive obtained in this comparative example may be referred to as "film adhesive (FR1)."

[0208] [Table 1]

[0209] [Table 2]

[0210] [Table 3]

[0211] As is clear from the above results, in Examples 1 to 6, after the film adhesive was cut by plasma irradiation and then cured with energy rays, the resulting silicon chip with the cured adhesive could be successfully picked up from the support sheet. In Examples 1 to 6, the peel force between the UV-cured film adhesive and the support sheet was 30 mN / 25 mm, which was small within an appropriate range. This result was consistent with the high pick-up properties of these Examples, as described above. In Examples 1 to 6, the gel fraction of the film adhesive upon plasma irradiation was 20% or less.

[0212] In Examples 1 to 6, the film adhesive G 23 ' was less than 1 MPa. In the film adhesives of Examples 1 to 6, the content of polymer component (a) relative to the total mass of the film adhesive was 38 mass % or less. The film adhesives of Examples 1 to 6 did not contain the filler (d).

[0213] In particular, the pick-up properties of the silicon chip with the cured adhesive were excellent in Examples 1, 3, and 4. In the film-like adhesives of Examples 1, 3, and 4, the content of polymer component (a) relative to the total mass of the film-like adhesive was particularly low, at 28 mass% or less. In Example 2, the content was also low at 10 mass%, but the film-like adhesive did not contain antioxidant (j1).

[0214] The film adhesives used in Examples 7, 8, and 9 were the same as the film adhesives used in Examples 1, 3, and 4, respectively. In Examples 7 to 9, the film-like adhesive was cured with energy rays to form a cured product, and then this energy ray-cured product was cut by irradiating it with plasma, 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, 3, 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 plasma irradiation. In Examples 1, 3, and 4, the gel fraction of the UV-cured film adhesive was low, at 19% or less. In Example 2, the gel fraction of the UV-cured film adhesive was also low at 16%, and it was therefore inferred that the film adhesive of Example 2 would also enable normal pickup of silicon chips with cured adhesive, regardless of whether the timing of energy ray irradiation was before or after plasma irradiation.

[0215] From the results of Examples 1, 3 to 6, it can be seen that the G 23 It was observed that the lower the G', the better the pick-up properties of the silicon chip with the cured adhesive. 23 ' was below 0.24 MPa.

[0216] In contrast, in Comparative Example 1, after the film adhesive was cut by plasma irradiation and then cured with energy rays, the pick-up properties of the silicon chip with the cured adhesive obtained were significantly inferior. In Comparative Example 1, the gel fraction of the film adhesive upon plasma irradiation was as high as 23%. In Comparative Example 1, the gel fraction of the UV-cured film adhesive was 30%, which was high. Therefore, it was inferred that the film adhesive of Comparative Example 1 would have poor pick-up properties for silicon chips with cured adhesive, regardless of whether the timing of energy ray irradiation was before or after plasma irradiation. [Industrial Applicability]

[0217] The present invention can be used in the manufacture of substrate devices. [Explanation of symbols]

[0218] 10: Support sheet; 10a: First surface of support sheet 101...Film adhesive composite sheet 11...Base material 13... Film-like adhesive, 13a... First surface of film-like adhesive

Claims

1. A film-like adhesive for cutting by plasma irradiation, the film-like adhesive is energy ray-curable, A film-like adhesive, wherein the film-like adhesive has a gel fraction of 22% or less.

2. The film-like adhesive according to claim 1 , wherein the film-like adhesive comprises an energy ray-curable component (g) and a photopolymerization initiator (h).

3. 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 25% or less.

4. 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 was measured. ２３ When the shear storage modulus G ２３ 3. The film adhesive according to claim 1 or 2, wherein the modulus of elasticity is 25 MPa or less.

5. 3. The film-like adhesive according to claim 1, wherein the content of the antioxidant (j1) relative to the total mass of the film-like adhesive is 0.1 to 5 mass%.

6. 3. The film-like adhesive according to claim 1, wherein the content of the polymer component (a) in the film-like adhesive is 40 mass % or less relative to the total mass of the film-like adhesive.

7. 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.

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

9. 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 9. The film-like adhesive composite sheet according to claim 7 or 8, 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.

10. A method for producing a chip with a cured adhesive using the film-like adhesive composite sheet according to claim 7 or 8, The chip with the cured adhesive material includes a chip and an energy ray-cured product of a film-like adhesive provided on one surface of the chip, In the manufacturing method, the film adhesive in the film adhesive composite sheet is attached to one side of a wafer, and the wafer and film adhesive are irradiated with plasma to divide the wafer into chips, and the film adhesive is cut and the film adhesive after cutting is cured with energy rays to produce a chip with the cured adhesive, and the chip with the cured adhesive is picked up by separating it from the support sheet.

11. A method for producing a chip with a cured adhesive using the film-like adhesive composite sheet according to claim 7 or 8, The chip with the cured adhesive material includes a chip and an energy ray-cured product of a film-like adhesive provided on one surface of the chip, the energy ray-cured product of the film-like adhesive has a gel fraction of 25% or less, In the manufacturing method, the film-like adhesive in the film-like adhesive composite sheet is attached to one side of a wafer, the attached film-like adhesive is cured with energy rays to form an energy ray-cured product, the wafer and the energy ray-cured product are irradiated with plasma to divide the wafer into chips, the energy ray-cured product is cut to produce chips with the adhesive-cured product, and the chips with the adhesive-cured product are separated from the support sheet and picked up.

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