Film-like adhesive, film-like adhesive composite sheet, and method for manufacturing a substrate device.

Abstract

To provide a film adhesive that can suppress misalignment of the position of a film adhesive composite sheet with a film adhesive relative to a ring frame, can sufficiently cut the energy ray cured product of the film adhesive by expansion, can suppress the scattering of the cured product, and can suppress the remaining voids between the thermosetting product and the circuit board when the chip is fixed to the circuit board by the thermosetting product. [Solution] Tg is 30°C or less, Tg of energy ray cured material is 30°C or higher, and probe tack value of energy ray cured material at 120°C is 1.2 N / cm 2 The above-described film-like adhesive 13, wherein when a laminate of the film-like adhesive 13 and a test substrate made of low-density polyethylene is prepared, and a weight of 3.5 g is attached to the end of the test substrate and maintained for 24 hours, the peel distance of the test substrate from the film-like adhesive 13 is less than 100 mm.

Description

[Technical Field]

[0001] The present invention relates to a film-like adhesive, a film-like adhesive composite sheet, and a method for manufacturing a substrate device. [Background technology]

[0002] In the manufacturing of semiconductor devices, for example, a semiconductor chip with an adhesive curing agent is manufactured, which comprises a semiconductor chip and an energy-ray cured film-like adhesive provided on the back surface of the semiconductor chip. This adhesive curing agent is then used to connect and fix the semiconductor chip to a circuit board for mounting. Film-like adhesives typically also have thermosetting properties, meaning they harden when heated. After bonding the semiconductor chip with the adhesive curing agent to the circuit board, the energy-ray curing agent is further heat-cured to fix the semiconductor chip to the circuit board.

[0003] For example, the following methods are known for manufacturing semiconductor devices (see Patent Document 1). Specifically, first, a film-like adhesive composite sheet is used, comprising a support sheet and a film-like adhesive provided on the support sheet. A group of semiconductor chips with a film-like adhesive composite sheet is then fabricated, in which multiple semiconductor chips are provided on the exposed surface of the film-like adhesive within the film-like adhesive composite sheet. The semiconductor chip group with the film-like adhesive composite sheet is fixed to the ring frame via an adhesive layer for the ring frame at the peripheral edge of the film-like adhesive within it. Next, under cooling conditions, the support sheet is expanded in a direction parallel to its surface, and the film-like adhesive is cut along the outer circumference of the semiconductor chip to produce a semiconductor chip with a film-like adhesive. Next, the semiconductor chip with the film-like adhesive is pulled away from the support sheet and picked up, then pressed onto the circuit board to connect the semiconductor chip to the circuit board. The film-like adhesive is then further heat-cured to fix the semiconductor chip to the circuit board. Thus, a semiconductor device is obtained.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] So far, as a typical example, the case has been described where a semiconductor chip with a film-like adhesive is picked up without curing the film-like adhesive with energy rays and the semiconductor chip is connected to a circuit board. However, as described above, there is a demand in the art for curing the film-like adhesive with energy rays, picking up a semiconductor chip with a cured adhesive, and connecting the semiconductor chip to a circuit board. Therefore, after fixing a group of semiconductor chips with a film-like adhesive composite sheet to a ring frame, when trying to adopt a series of steps of curing the film-like adhesive with energy rays and then cutting the energy ray-cured product of the film-like adhesive by expansion, if the group of semiconductor chips with the film-like adhesive composite sheet is left for a long time such as 24 hours or more in a state fixed to the ring frame, there is a problem that the width of the film-like adhesive composite sheet may shrink and the arrangement position of the film-like adhesive composite sheet with respect to the ring frame may shift. Such a shift in the arrangement position is presumably because the group of semiconductor chips with the film-like adhesive composite sheet is fixed to the ring frame while tension is applied in the width direction to the film-like adhesive composite sheet. However, in this case, the film-like adhesive composite sheet may be wrinkled or sagged, which hinders the manufacture of the semiconductor device.

[0006] Furthermore, in the above method of energy ray-curing the film-shaped adhesive, there was a problem that during expansion, the cutting of the energy ray-cured product of the film-shaped adhesive might be insufficient. Further, there was also a problem that small pieces of the cured product scattered in the region near the peripheral portion of the cured product where the semiconductor chip was not provided. Such scattered cured products adhered to the semiconductor chip, which hindered the manufacturing of the semiconductor device.

[0007] Furthermore, in the above method of energy ray-curing the film-shaped adhesive, after pressing the semiconductor chip with the cured adhesive onto the circuit board and thermally curing the cured adhesive, there was a problem that voids might remain between the thermally cured product of the cured adhesive and the circuit board. When such voids remained, the reliability of the semiconductor device was impaired.

[0008] So far, the case of manufacturing a semiconductor device has been taken as an example to explain the problems at that time. However, similar problems can also occur when manufacturing a substrate device other than a semiconductor device from a chip other than a semiconductor chip.

[0009] The present invention uses a film-shaped adhesive composite sheet provided with a film-shaped adhesive having energy ray-curability and thermosetting properties, connects and fixes a chip to a circuit board, and during the manufacture of the substrate device, fixes a group of chips with the film-shaped adhesive composite sheet to a ring frame through an adhesive layer for the ring frame. When left standing, the displacement of the arrangement position of the film-shaped adhesive composite sheet with respect to the ring frame can be suppressed. During expansion, the energy ray-cured product of the film-shaped adhesive can be sufficiently cut, and the scattering of the cured product in the region near its peripheral portion can be suppressed. After pressing the chip with the cured adhesive onto the circuit board and thermally curing the cured adhesive, the remaining of voids can be suppressed between the thermally cured product of the cured adhesive and the circuit board. The purpose is to provide a film-shaped adhesive.

Means for Solving the Problem

[0010] To solve the above problems, the present invention employs the following configuration. [1] A film-like adhesive having energy ray curing and thermosetting properties, The glass transition temperature Tg1 of the aforementioned film-like adhesive is 30°C or lower. The glass transition temperature Tg2 of the energy-ray cured product of the aforementioned film-like adhesive is 30°C or higher. The probe tack value t1 of the energy-ray cured film adhesive is 1.2 N / cm at 120°C. 2 That's all. A test piece measuring 25 mm in width and 150 mm in length is made of the aforementioned film-like adhesive and a test substrate made of low-density polyethylene with a thickness of 80 μm. This piece is attached to a silicon wafer using the film-like adhesive in the test piece at an attachment speed of 20 mm / s, an attachment pressure of 0.375 MPa, and an attachment temperature of 40°C. Next, a portion of the test substrate up to 50 mm from one end is peeled from the film-like adhesive, and a weight of 3.5 g is attached to the end of the peeled test substrate to create a test laminate. The test laminate is then fixed by holding the silicon wafer within the test laminate with the test substrate facing vertically downwards, and tension is applied to the test substrate from the weight. This state is maintained at room temperature for 24 hours. Then, the length L of the portion of the test substrate in the test laminate that has not been peeled from the film-like adhesive is measured. R A peel test is performed to measure the following formula (i) [Peeling distance of test substrate] = 100 - L R (i) A film-like adhesive in which, when the peeling distance of the test substrate is calculated by the method described above, the peeling distance is less than 100 mm.

[0011] [2] The film-like adhesive according to [1], wherein the probe tack integral value e1 of the energy-ray cured film-like adhesive at 120°C is 0.225 N·s or more. [3] A film-like adhesive composite sheet comprising a base material and a film-like adhesive provided on one surface of the base material, wherein the film-like adhesive is the film-like adhesive described in [1] or [2].

[0012] A method for manufacturing a substrate device using the film-like adhesive composite sheet described in [4] [3], The aforementioned substrate device is configured such that the chip is connected to and fixed to the circuit board. In the above manufacturing method, a group of chips with a film-like adhesive composite sheet, comprising the film-like adhesive composite sheet and a plurality of chips held on the exposed surface of the film-like adhesive in the film-like adhesive composite sheet, is fixed to a ring frame via a ring frame adhesive layer at the peripheral edge of the film-like adhesive. In an atmosphere containing oxygen, the film-like adhesive in the chip group with the fixed film-like adhesive composite sheet is irradiated with energy rays through the substrate to produce an energy-ray cured product of the film-like adhesive. Under cooling conditions, after irradiation with the energy rays, the substrate is expanded in a direction parallel to the side of the substrate where the energy ray cured material is located, and the energy ray cured material is cut along the outer circumference of the tip, thereby producing a chip with an adhesive cured material, comprising the tip and the energy ray cured material of the film-like adhesive after cutting, which is provided on the back surface of the tip. A method for manufacturing a substrate device, comprising: pulling the adhesive-cured chip away from the substrate and picking it up; pressing the chip onto the circuit board using the energy ray curing material to connect the chip in the adhesive-cured chip to the circuit board; and further thermally curing the energy ray curing material after connection to fix the chip to the circuit board. [Effects of the Invention]

[0013] According to the present invention, a film-like adhesive composite sheet is provided that allows for the connection and fixing of chips to a circuit board using an energy-ray curable and thermosetting film-like adhesive composite sheet. During the manufacturing of the circuit board device, the chip group with the film-like adhesive composite sheet is fixed to the ring frame via an adhesive layer for the ring frame and left unattended. This suppresses displacement of the film-like adhesive composite sheet relative to the ring frame, and during expansion, it allows for sufficient cutting of the energy-ray cured portion of the film-like adhesive, while suppressing scattering of the cured portion in the area near its periphery. After the chip with the cured adhesive is pressed to the circuit board and the cured adhesive is thermoset, the remaining voids between the thermoset portion of the cured adhesive and the circuit board are suppressed. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic cross-sectional view showing an example of a film-like adhesive according to one embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view illustrating a method for measuring the peel distance in a peel test of a film-like adhesive according to one embodiment of the present invention. [Figure 3] This is a schematic cross-sectional view showing an example of a film-like adhesive composite sheet according to one embodiment of the present invention. [Modes for carrying out the invention]

[0015] ◇Film-type adhesive A film-like adhesive according to one embodiment of the present invention has energy ray curability and thermosetting properties. The glass transition temperature Tg1 of the aforementioned film-like adhesive (sometimes simply referred to as "Tg1" in this specification) is 30°C or lower. The glass transition temperature Tg2 (sometimes simply referred to as "Tg2" in this specification) of the energy-ray cured product of the aforementioned film-like adhesive is 30°C or higher. The probe tack value t1 (sometimes simply referred to as "t1" in this specification) of the energy-ray cured film adhesive is 1.2 N / cm². 2 As described above, a test piece with a width of 25 mm and a length of 150 mm, which is a laminate of the film-like adhesive and a test substrate made of low-density polyethylene with a thickness of 80 μm, is attached to a silicon wafer using the film-like adhesive in the test piece under the conditions of attachment speed of 20 mm / s, attachment pressure of 0.375 MPa, and attachment temperature of 40°C. Next, a portion of the test substrate from one end up to 50 mm is peeled from the film-like adhesive, and a weight of 3.5 g is attached to the end of the peeled test substrate to create a test laminate. The test substrate in the test laminate is oriented vertically downward, and the silicon wafer in the test laminate is held in place to fix the test laminate, and tension from the weight on the test substrate is started and this state is maintained at room temperature for 24 hours. Then, the length L of the portion of the test substrate in the test laminate that has not been peeled from the film-like adhesive is measured. R A peel test is performed to measure the following formula (i) [Peeling distance of test substrate] = 100 - L R (i) When the peeling distance of the test substrate is calculated using this method, the peeling distance is less than 100 mm.

[0016] The film-like adhesive of this embodiment can be laminated with a substrate to form a film-like adhesive composite sheet, as described later. This film-like adhesive composite sheet can be used in the same way as known dicing die bonding sheets. The film-like adhesive of this embodiment can be used to manufacture a substrate device in the manufacturing method described later, by forming the film-like adhesive composite sheet.

[0017] Because the Tg1 of the aforementioned film-like adhesive is 30°C or lower, when using a film-like adhesive composite sheet (sometimes referred to as a "cured composite sheet" in this specification) after energy ray curing of the film-like adhesive, and expanding the substrate in an atmosphere of oxygen (oxygen gas), scattering of the energy ray cured film-like adhesive in the area near its peripheral edge can be suppressed. Furthermore, because the Tg2 of the energy-ray cured film adhesive is 30°C or higher, the energy-ray cured film adhesive can be sufficiently cut during the expansion of the substrate. In this embodiment, the degree of ease of cutting the film adhesive or its energy-ray cured product during expansion may be referred to as "cuttability". Furthermore, the energy ray cured film adhesive has a t1 of 1.2 N / cm² at 120°C. 2 As a result of the above, after the adhesive-cured chip is pressed onto the circuit board and the adhesive is heat-cured, the remaining voids between the heat-cured adhesive and the circuit board can be suppressed. Furthermore, by making the peeling distance of the film-like adhesive less than 100 mm, when the chip group with the film-like adhesive composite sheet is fixed to the ring frame via the adhesive layer for the ring frame and left to stand, even if the standing time is long, such as 24 hours or more, displacement of the position of the film-like adhesive composite sheet relative to the ring frame can be suppressed. And, the larger the t1 of the energy ray cured product of the film-like adhesive, the shorter the peeling distance can be made.

[0018] In this specification, "adhesive-cured chip" means a structure comprising a chip and an energy-ray cured film-like adhesive provided on the back surface of the chip.

[0019] In this specification, "film adhesive" means a film adhesive that has not undergone both intentional energy ray curing and intentional thermal curing, unless otherwise specified. Unless otherwise specified, "cured adhesive product" refers to an energy-ray cured product of a film-type adhesive. Therefore, unless otherwise specified, the thermosetting product of the cured adhesive described below refers to a cured product obtained by further thermosetting an energy-ray cured product obtained by energy-ray curing of a film-type adhesive.

[0020] In this specification, the wafers include semiconductor wafers composed of elemental semiconductors such as silicon, germanium, and selenium, and compound semiconductors such as GaAs, GaP, InP, CdTe, ZnSe, and SiC; and insulating wafers composed of insulators such as sapphire and glass. For example, if the wafer is a semiconductor wafer, then the chip would be a semiconductor chip. One side of a wafer is the circuit side, on which the circuit is formed, and the side opposite to this is referred to as the "back side" in this specification. The same applies to chips; the side of a chip opposite to the circuit side on which the circuit is formed is referred to as the "back side." Both the circuit surface of the wafer and the circuit surface of the chip are provided with protruding electrodes such as bumps and pillars.

[0021] In this specification, "substrate device" means a device constructed by connecting and fixing an adhesive-cured chip to a circuit board using the adhesive. For example, if a semiconductor wafer is used as the wafer, a semiconductor device can be considered a substrate device.

[0022] In this specification, "energy ray" means an electromagnetic wave or charged particle beam that has an energy quantum, and examples include ultraviolet rays, radiation, electron beams, etc. In this specification, "energy ray curability" means the property of hardening when irradiated with energy rays. In this specification, "thermosetting" means the property of hardening upon heating.

[0023] When the energy ray-cured product of the film-shaped adhesive is actually used, the curing conditions for curing the film-shaped adhesive with energy rays are not particularly limited as long as the degree of cure of the cured product is sufficiently high, and may be appropriately selected according to the type of the film-shaped adhesive. Usually, when curing the film-shaped adhesive with energy rays, the illuminance of the energy rays is preferably 60 to 320 mW / cm 2 and the light quantity of the energy rays is preferably 100 to 1000 mJ / cm 2

[0024] FIG. 1 is a cross-sectional view schematically showing an example of the film-shaped adhesive of the present embodiment. In addition, the figures used in the following description may show the main part enlarged for the sake of clarity of the features of the present invention, and the dimensional ratios of each component are not necessarily the same as the actual ones.

[0025] The film-shaped adhesive 13 shown in FIG. 1 has a first release film 151 on one surface (which may be referred to as the "first surface" in this specification) 13a thereof, and a second release film 152 on the other surface (which may be referred to as the "second surface" in this specification) 13b opposite to the first surface 13a. Such a film-shaped adhesive 13 is suitable for storage in a roll shape, for example.

[0026] The film-shaped adhesive 13 has energy ray curability and heat curability. The glass transition temperature Tg1 of the film-shaped adhesive 13 is 30°C or lower. The glass transition temperature Tg2 of the energy ray-cured product of the film-shaped adhesive 13 is 30°C or higher, and the probe tack value t1 at 120°C is 1.2 N / cm 2 or higher. When the test laminate is produced using the film-shaped adhesive 13 and the measured peeling distance is less than 100 mm. These physical properties of the film-shaped adhesive 13 will be described in detail later.

[0027] ​ The first release film 151 and the second release film 152 may both be known. The first release film 151 and the second release film 152 may be the same as each other, or they may be different from each other, for example, having different peeling forces required to peel them off the film-like adhesive 13.

[0028] Either the first surface 13a or the second surface 13b of the film-like adhesive 13 becomes the surface for attaching to the back surface of the chip, and the other becomes the surface for attaching to the substrate, which will be described later.

[0029] <<Peel distance in peel tests of film-like adhesives>> The method for measuring the peel distance in the peel test of the film-like adhesive will be explained in more detail with reference to Figure 2. First, as shown in Figure 2(a), a test specimen 30 is prepared, which is a laminate of a film-like adhesive 13 and a test substrate 8 made of low-density polyethylene with a thickness of 80 μm. The film-like adhesive 13 is the film-like adhesive 13 shown in Figure 1.

[0030] Length L of test specimen 30 30 The length is 150 mm, and the length of the film-like adhesive 13 and the length of the test substrate 8 are either the same as each other, or if they are different, the difference is so small that they can be considered to be the same in appearance. The width of the test specimen 30 (i.e., the dimension of the test specimen 30 in the direction perpendicular to its cross-section in Figure 2(a)) is 25 mm, and the width of the film-like adhesive 13 and the width of the test substrate 8 are either the same as each other, or if they are different, the difference is so small that they can be considered to be the same in appearance.

[0031] Next, as shown in Figure 2(b), the test piece 30 is attached to the silicon wafer 9 using the film-like adhesive 13 contained within the test piece 30. The attachment speed at this time is 20 mm / s, the attachment pressure is 0.375 MPa, and the attachment temperature (in other words, the heating temperature of the test piece 30) is 40°C.

[0032] Next, as shown in Figure 2(c), the portion of the test substrate 8 up to 50 mm from one end is peeled off from the film-like adhesive 13. That is, at this stage, the length L of the portion of the test substrate 8 that has not been peeled off from the film-like adhesive is... 80 This will be 100mm. Furthermore, a test laminate 6 is prepared by attaching a weight 7 with a mass of 3.5 g to the end of the test substrate 8 after peeling. Before the start of the peel test, the length of the peeled portion from the film-like adhesive 13 of the test substrate 8 in the test laminate 6 should not exceed 50 mm (L 80 Adjust so that it does not fall below 100mm.

[0033] Next, the test laminate 6 is fixed by orienting the test substrate 8 in the test laminate 6 vertically downward (as is already done in Figure 2(c)) and holding the silicon wafer 9 in the test laminate 6. At this time, in order to avoid adverse effects in the subsequent peel test, the holding means is not in contact with the film-like adhesive 13 and the test substrate 8 in the test laminate 6, but the holding means is in contact with the silicon wafer 9. At this time, for example, the weight 7 is held separately to prevent tension from being generated on the test substrate 8 from the weight 7.

[0034] Next, at room temperature (for example, 23°C), the weight 7 is released, initiating tension from the weight 7 onto the test substrate 8 and starting the peel test. This state of the test substrate 8 being pulled by the weight 7 is then maintained at room temperature for 24 hours. During this time, the length of the peeled portion of the test substrate 8 from the film-like adhesive 13 does not change, or does not exceed 50 mm (L). 80 (This will remain at 100mm, or become shorter than 100mm.)

[0035] In this specification, "room temperature" means a temperature that is neither cooled nor heated, i.e., a normal temperature, such as 18-28°C.

[0036] At 24 hours after the start of the peel test, the length L of the portion of the test substrate 8 that has not peeled from the film-like adhesive 13, as shown in Figure 2(d), is measured. R (0≦L R Measure (≤100). Then, according to the following formula (i), L R The peeling distance of the test substrate 8 is calculated using this method. [Peeling distance of test substrate] = 100 - L R (i)

[0037] In this embodiment, the peeling distance is less than 100 mm, and may be, for example, 90 mm or less, 60 mm or less, 30 mm or less, 15 mm or less, or 5 mm or less. The shorter the peeling distance, the greater the effect of suppressing misalignment of the film-like adhesive composite sheet relative to the ring frame. A peeling distance of less than 100 mm means that the test substrate 8 does not separate from the film-like adhesive 13. On the other hand, the peeling distance is 0 mm or more.

[0038] <<Glass transition temperature Tg1 of film-like adhesives>> The glass transition temperature Tg1 of the film-like adhesive is 30°C or lower, and may be, for example, 29°C or lower, or 28°C or lower. The lower the Tg1, the greater the effect of suppressing the scattering of energy-ray cured material of the film-like adhesive during the expansion process described above. On the other hand, the lower limit of Tg1 is not particularly limited. For example, a film-like adhesive with a Tg1 of -10°C or higher can be more easily realized. In one embodiment, Tg1 may be, for example, -10 to 30°C, -10 to 29°C, and -10 to 28°C. However, these are just examples of Tg1.

[0039] In this embodiment, the glass transition temperature Tg1 of the film adhesive refers to the glass transition temperature of the film adhesive measured under an air atmosphere.

[0040] The glass transition temperature Tg1 of a film-type adhesive can be adjusted by adjusting the type or amount of components contained in the film-type adhesive. In particular, Tg1 can be adjusted more easily by adjusting the type or amount of the polymer component (a), epoxy resin (b1), and energy ray curable component (g) contained in the film-type adhesive, as described below. For example, Tg1 can be lowered more easily by selecting a monomer that does not have a high glass transition temperature for its homopolymer (e.g., a monomer with a temperature of 0°C or lower) as the monomer that induces the constituent units in the polymer component (a), by using an epoxy resin (b1) that is liquid at room temperature, or by increasing the content of such polymer component (a) or epoxy resin (b1).

[0041] <<Glass transition temperature (Tg2) of energy-ray cured film-type adhesives>> The glass transition temperature Tg2 of the energy-ray cured film adhesive is 30°C or higher, and may be, for example, 31°C or higher, 34°C or higher, or 36°C or higher. The higher the Tg2, the better the cleavage of the energy-ray cured film adhesive during the expansion process described above. On the other hand, the upper limit of Tg2 is not particularly limited. For example, a film-like adhesive with a Tg2 of 120°C or less can be more easily realized. In one embodiment, Tg2 may be, for example, 30-120°C, 31-120°C, 34-120°C, and 36-120°C. However, these are just examples of Tg2.

[0042] In this embodiment, the glass transition temperature Tg2 of the energy-ray cured film adhesive is defined as an illuminance of 230 mW / cm² in an air atmosphere. 2 , light intensity 190mJ / cm 2 This refers to the glass transition temperature measured in an air atmosphere of an energy-ray cured product obtained by irradiating a film-like adhesive with energy rays under the specified conditions.

[0043] The Tg2 of an energy-ray cured film adhesive can be adjusted by adjusting the type or amount of components contained in the film adhesive. In particular, Tg2 can be adjusted more easily by adjusting the type or amount of the polymer component (a), epoxy resin (b1), and energy-ray curable component (g) contained in the film adhesive, as described below. For example, Tg2 can be increased more easily by selecting an energy-ray curable component (g) with a high glass transition temperature, using an epoxy resin (b1) that is solid at room temperature, or increasing the content of such energy-ray curable component (g) or epoxy resin (b1).

[0044] <<Probe tack value t1 at 120°C for energy-ray cured film adhesive>> The probe tack value t1 at 120°C for energy-ray cured film adhesive is 1.2 N / cm 2 (122.4 gf / cm²) 2 ) or more, for example, 1.35 N / cm² 2 (137.7 gf / cm 2 ) Above 1.45 N / cm 2 (147.9 gf / cm²) 2 ) or more, and 1.5 N / cm 2 (153 gf / cm³) 2 ) Any of the above may be used. The larger t1 is, the greater the effect of suppressing the remaining voids between the thermoset product of the adhesive curing material and the circuit board, and the greater the effect of suppressing the displacement of the position of the film-like adhesive composite sheet relative to the ring frame. On the other hand, the upper limit of t1 is not particularly limited. For example, if t1 is 3N / cm 2 (305.9 gf / cm²) 2 The handling properties of film-type adhesives that are as follows are better. In one embodiment, t1 is, for example, 1.2 to 3 N / cm 2 , 1.35~3N / cm 2 , 1.45~3N / cm 2 , and 1.5~3N / cm 2 It may be any of the following; however, these are just examples of t1.

[0045] <<Integrated probe tack value e1 at 120°C for energy-ray cured film-type adhesive>> In this embodiment, the probe tack integral value e1 of the energy-ray cured film adhesive at 120°C is preferably 0.225 N·s (22.9 gf·s) or higher. When e1 is above the lower limit, t1 is 1.2 N / cm 2 The same effect can be obtained as in the above cases.

[0046] In terms of achieving the above-mentioned effects, namely the effect of suppressing the remaining voids between the thermoset adhesive cured product and the circuit board, and the effect of suppressing the displacement of the film-like adhesive composite sheet relative to the ring frame, e1 may be, for example, 0.26 N·s (26.5 gf·s) or higher, 0.29 N·s (29.6 gf·s) or higher, and 0.32 N·s (32.6 gf·s) or higher. On the other hand, the upper limit of e1 is not particularly limited. For example, film-type adhesives with e1 of 0.5 N·s (51.0 gf·s) or less have better handling properties. In one embodiment, the energy ray cured product e1 of the film-like adhesive may be, for example, 0.225 to 0.5 N·s, 0.26 to 0.5 N·s, 0.29 to 0.5 N·s, and 0.32 to 0.5 N·s. However, these are just examples of e1.

[0047] In this embodiment, the probe tack value t1 and the probe tack integral value e1 of the energy-ray cured film-like adhesive were determined, respectively, under an air atmosphere with an illuminance of 230 mW / cm². 2 , light intensity 190mJ / cm 2 This refers to the probe tack value and probe tack integral value at 120°C, measured in an air atmosphere, of an energy-ray cured product obtained by irradiating a film-like adhesive with energy rays under the specified conditions.

[0048] In the film-like adhesive of this embodiment (energy-ray cured film-like adhesive), it is preferable that both the probe tack value t1 and the probe tack integral value e1 are within any of the above-mentioned numerical ranges.

[0049] <<An example of a film-type adhesive>> The film adhesive of this embodiment preferably contains a thermosetting component (b) and an energy ray curable component (g), and more preferably contains a thermosetting component (b), a curing accelerator (c), an energy ray curable component (g), and a photopolymerization initiator (h). In terms of having good film-forming properties, the film-like adhesive of this embodiment is preferably further containing polymer component (a). The components of the film-like adhesive in this embodiment will be described in detail later.

[0050] The film-like adhesive may consist of one layer (single layer) or of two or more layers. If the film-like adhesive consists of multiple layers, these layers may be identical or different from each other, and there are no particular limitations on the combination of these layers.

[0051] In this specification, not only in the case of film-like adhesives, "multiple layers may be identical or different from one another" means "all layers may be identical, all layers may be different, or only some layers may be identical," and further, "multiple layers are different from one another" means "at least one of the constituent materials and thickness of each layer is different from the other."

[0052] The thickness of the film-like adhesive is preferably 1 to 70 μm, more preferably 2 to 50 μm, and even more preferably 3 to 30 μm. When the thickness of the film-like adhesive is above the lower limit, the strength of the film-like adhesive is increased, and the effects obtained by using the film-like adhesive are also increased. When the thickness of the film-like adhesive is below the upper limit, it is avoided that the thickness of the film-like adhesive and its cured product becomes excessive. Here, "thickness of the film adhesive" refers to the total thickness of the film adhesive. For example, the thickness of a multi-layered film adhesive refers to the total thickness of all the layers that make up the film adhesive. This also applies to other layers such as the substrate, which will be discussed later.

[0053] In this specification, unless otherwise specified, "thickness" refers to the average of the thicknesses measured at five randomly selected locations on the object, and can be obtained using a constant-pressure thickness measuring instrument in accordance with JIS K7130.

[0054] <<Adhesive Composition>> The aforementioned film-like adhesive can be formed using an adhesive composition containing its constituent materials. For example, the adhesive composition can be applied to the surface to which the film-like adhesive is to be formed using a known method, and dried as necessary, thereby forming the film-like adhesive in the desired area. The ratio of components that do not vaporize at room temperature in an adhesive composition is usually the same as the ratio of those components in a film-type adhesive.

[0055] In a film-like adhesive, the ratio of the total content of one or more of the components described later in the film-like adhesive to the total mass of the film-like adhesive shall not exceed 100% by mass. Similarly, in an adhesive composition, the ratio of the total content of one or more of the components described later in the adhesive composition to the total mass of the adhesive composition shall not exceed 100% by mass.

[0056] The drying conditions for the adhesive composition are not particularly limited, but if the adhesive composition contains a solvent as described later, it is preferable to heat dry it. For example, adhesive compositions containing a solvent are preferably dried at 70 to 130°C for 10 seconds to 5 minutes. The components of the film-type adhesive and adhesive composition will be described in detail below.

[0057] Examples of the adhesive composition include a composition containing a polymer component (a), a thermosetting component (b), and an energy ray curable component (g) (which may be abbreviated as "composition (III)" in this specification), and it is preferable that the adhesive composition further contains either or both of a curing accelerator (c) and a photopolymerization initiator (h).

[0058] The polymer component (a), thermosetting component (b), curing accelerator (c), energy ray curable component (g), and photopolymerization initiator (h) contained in composition (III) and the film-like adhesive may each consist of only one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0059] <polymer component (a)> Polymer component (a) is a component that can be considered to have been formed by a polymerization reaction of polymerizable compounds, and is a polymer compound for imparting film-forming properties, flexibility, etc., to film-like adhesives. In this specification, polymer compounds also include products of polycondensation reactions.

[0060] Examples of polymer component (a) include acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin, etc., with acrylic resin being preferred.

[0061] Examples of the acrylic resin in polymer component (a) include known acrylic polymers. 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, 300,000 to 1,000,000. Having the weight-average molecular weight of the acrylic resin within this range makes it easy to adjust the adhesive strength between the film-like adhesive and the adherend to a preferred range. Furthermore, it becomes easy to adjust the glass transition temperature Tg1 of the film-like adhesive, as well as the glass transition temperature Tg2 and probe tack value t1 of the energy-ray cured product of the film-like adhesive, to the desired range. On the other hand, if the weight-average molecular weight of the acrylic resin is above the lower limit, it has the effect of suppressing the generation of voids between the film-like adhesive and the adherend, and the shape stability (stable over time during storage) of the film-like adhesive is improved. If the weight-average molecular weight of the acrylic resin is below the upper limit, the surface condition of the coated object becomes more stable when the adhesive composition is applied to the object to which the film-like adhesive is formed, and the film-like adhesive becomes more able to conform to the uneven surface of the adherend.

[0062] In this specification, "weight-average molecular weight" refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC) unless otherwise specified.

[0063] The constituent units of the acrylic resin may consist of only one type, or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0064] The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70°C, more preferably -45 to 50°C, and may also be, for example, -35 to 30°C. When the Tg of the acrylic resin is above the lower limit, the adhesive strength between the film-like adhesive and the adherend is suppressed, making it easier to pick up the adhesive-cured chip from the substrate, as described later. When the Tg of the acrylic resin is below the upper limit, the adhesive strength between the film-like adhesive and the chip is improved.

[0065] When an acrylic resin has two or more constituent units, the glass transition temperature (Tg) of the acrylic resin can be calculated using Fox's formula. The Tg of the homopolymer of the monomers that derive the constituent units can be the value specified in the Polymer Data Handbook, Adhesion Handbook, or Polymer Handbook.

[0066] Examples of acrylic resins include polymers of one or more (meth)acrylic acid esters; and copolymers of two or more monomers selected from the (meth)acrylic acid esters, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.

[0067] In this specification, "(meth)acrylic acid" is a concept that encompasses both "acrylic acid" and "methacrylic acid." This also applies to terms similar to (meth)acrylic acid, such as (meth)acryloyl group.

[0068] Examples of the (meth)acrylic acid esters constituting the acrylic resin include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, in which the alkyl group constituting the alkyl ester has a chain structure with 1 to 18 carbon atoms; cycloalkyl (meth)acrylates 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.

[0069] The acrylic resin may or may not have functional groups that can bond to other compounds, such as vinyl groups, (meth)acryloyl groups, amino groups, carboxyl groups, and isocyanate groups, in addition to the hydroxyl groups mentioned above. The functional groups of the acrylic resin may be bonded to other compounds via a crosslinking agent (f) described later, or they may be directly bonded to other compounds without the crosslinking agent (f).

[0070] In a film-like adhesive, the ratio of the polymer component (a) content to the total mass of the film-like adhesive is preferably 30% by mass or less, regardless of the type of polymer component (a), and may be, for example, 25% by mass or less, 20% by mass or less, 17% by mass or less, or 14% by mass or less. By keeping the ratio below the upper limit, it becomes easier to adjust the degree of the effect obtained by using components other than polymer component (a). On the other hand, the aforementioned ratio is more than 0% by mass, and it is preferable that it be 6% by mass or more in that the effect obtained by using polymer component (a) is further enhanced.

[0071] The above-mentioned provision regarding the ratio of polymer component (a) content to the total mass of the film-like adhesive means that, in composition (III), the ratio of polymer component (a) content to the total content of all components other than the solvent is preferably 30% by mass or less, regardless of the type of polymer component (a), for example, it may be 25% by mass or less, 20% by mass or less, 17% by mass or less, or 14% by mass or less, while the aforementioned ratio is preferably greater than 0% by mass and 6% by 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 ratio of the contents of non-solvent components is the same in the resin composition and the resin film. Therefore, in this specification, not limited to the case of film-like adhesives, the content of non-solvent components will mainly refer to the content in the resin film obtained by removing the solvent from the resin composition.

[0072] <Thermosetting component (b)> Thermosetting component (b) is a component that has thermosetting properties and is used to heat-cur 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, thermosetting polyimide resin is a general term encompassing a polyimide precursor and a thermosetting polyimide, both of which form a polyimide resin through thermosetting.

[0073] [Epoxy thermosetting resin] The epoxy-based thermosetting resin comprises an epoxy resin (b1) and a thermosetting agent (b2). The epoxy resin (b1) and thermosetting agent (b2) contained in composition (III) and the film-like adhesive may each consist of only one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0074] (Epoxy resin (b1)) Examples of epoxy resins (b1) include well-known ones, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, orthocresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and other bifunctional or more epoxy compounds.

[0075] The number-average molecular weight of the epoxy resin (b1) is not particularly limited, but is preferably 300 to 30000 from the viewpoint of the curability of the film-like adhesive and the strength and heat resistance of the cured product of the film-like adhesive. The epoxy equivalent of epoxy resin (b1) is preferably 100 to 1000 g / eq, and may be, for example, 100 to 600 g / eq and 150 to 300 g / eq.

[0076] The composition (III) and the film-like adhesive preferably contain a dicyclopentadiene type epoxy resin and a bisphenol F type epoxy resin as the epoxy resin (b1). The inclusion of such a combination of epoxy resins (b1) in the film-like adhesive improves the pickability of the adhesive-cured chip and facilitates the manufacturing of the substrate device.

[0077] 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 25 to 50 times the mass of the content of the bisphenol F type epoxy resin. For example, it may be 25 to 46 times and 25 to 42 times, or 30 to 50 times and 34 to 50 times, or 30 to 46 times and 34 to 42 times. Satisfying these conditions enhances the effects obtained by the film-like adhesive containing both the dicyclopentadiene type epoxy resin and the bisphenol F type epoxy resin.

[0078] When composition (III) and the film-like adhesive contain a dicyclopentadiene-type epoxy resin and a bisphenol F-type epoxy resin, the ratio of the total content of the dicyclopentadiene-type epoxy resin and the bisphenol F-type epoxy resin to the content of epoxy resin (b1) in composition (III) and the film-like adhesive is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, for example, it may be 90% by mass or more, 93% by mass or more, and 96% by mass or more. When the ratio is above the lower limit, the effects obtained by the film-like adhesive containing the dicyclopentadiene-type epoxy resin and the bisphenol F-type epoxy resin are significantly enhanced. On the other hand, the ratio is 100% by mass or less.

[0079] (Thermosetting agent (b2)) The thermosetting agent (b2) is a curing agent for epoxy resin (b1). Examples of the thermosetting agent (b2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional groups include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and groups in which an acid group has been converted to an anhydride. It is preferable that the functional group is a phenolic hydroxyl group, an amino group, or a group in which an acid group has been converted to an anhydride, and more preferably a phenolic hydroxyl group or an amino group.

[0080] Examples of thermosetting agents (b2) that include phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenolic resins, biphenols, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins. Examples of amine-based curing agents containing an amino group among the thermosetting agents (b2) include dicyandiamide (DICY).

[0081] The hydroxyl group equivalent of the thermosetting agent (b2) is preferably 10 to 120 g / eq, and may be, for example, 10 to 60 g / eq and 10 to 40 g / eq.

[0082] Among the thermosetting agents (b2), the number average molecular weight of the resin components, such as polyfunctional phenolic resins, novolac-type phenolic resins, dicyclopentadiene-type phenolic resins, and aralkyl-type phenolic resins, is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000. The molecular weight of the non-resin component of the thermosetting agent (b2), such as biphenol or dicyandiamide, is not particularly limited, but is preferably 60 to 500.

[0083] In composition (III) and the film-like adhesive, the content of the thermosetting agent (b2) is preferably 1 to 10 parts by mass per 100 parts by mass of the epoxy resin (b1), and may be, for example, 1 to 8 parts by mass, 1 to 6 parts by mass, or 1 to 3.5 parts by mass. When the content of the thermosetting agent (b2) is above the lower limit, the thermal curing of the film-like adhesive proceeds more easily. When the content of the thermosetting agent (b2) is below the upper limit, the moisture absorption rate of the film-like adhesive is reduced, and the reliability of the package obtained using the film-like adhesive is further improved.

[0084] In composition (III) and the film-like adhesive, the content of the thermosetting component (b) (for example, the total content of epoxy resin (b1) and thermosetting agent (b2)) is preferably 100 to 1000 parts by mass, more preferably 250 to 1000 parts by mass, per 100 parts by mass of the polymer component (a). For example, it may be any of 400 to 1000 parts by mass and 550 to 1000 parts by mass, or any of 250 to 900 parts by mass and 250 to 850 parts by mass, or any of 400 to 900 parts by mass and 550 to 850 parts by mass. Having the content of the thermosetting component (b) within such a range makes it easier to adjust the adhesive strength between the film-like adhesive and the substrate described later.

[0085] <Energy ray curing component (g)> The energy ray curable component (g) facilitates the pickup of the adhesive-cured chip from the substrate. Examples of energy ray-curable components (g) include energy ray-curable nonpolymers (sometimes referred to as "energy ray-curable nonpolymer (g1)" in this specification) and energy ray-curable oligomers or polymers (polymers) (sometimes referred to as "energy ray-curable polymer (g2)" in this specification).

[0086] [Energy ray curable nonpolymer (g1)] The aforementioned energy-ray curable nonpolymer (g1) cannot be considered a monomer polymer and is a component that possesses energy-ray curability. Examples of energy-ray curable nonpolymers (g1) include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth)acryloyl group are preferred.

[0087] Examples of the aforementioned acrylate compounds include (meth)acrylates containing a chain-like aliphatic skeleton such as 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 cyclic aliphatic skeleton such as dicyclopentanyl di(meth)acrylate and tricyclodecane dimethylol diacrylate; oligoester (meth)acrylates; and epoxy-modified (meth)acrylates.

[0088] [Energy ray curable polymer (g2)] The energy-curable polymer (g2) may or may not be crosslinked with a crosslinking agent in at least a portion of its structure.

[0089] Examples of energy-ray curable polymers (g2) include: An acrylic polymer (g21) having a functional group that can react with groups of other compounds, and an energy-ray curable compound (g22) having a reactive group that reacts with the functional group and an energy-ray curable group such as an energy-ray curable double bond, resulting in an energy-ray curable acrylic resin (g2-1) having a structure in which the functional group and the reactive group react; Polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; Polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylate; Examples include urethane (meth)acrylate oligomers and itaconic acid oligomers.

[0090] Of the energy-curable polymers (g2), the weight-average molecular weight of the energy-curable acrylic resin (g2-1) is preferably 20,000 to 2,000,000, and may be any of the following: 20,000 to 1,000,000, 20,000 to 500,000, 20,000 to 300,000, and 20,000 to 100,000. Of the energy-curable polymer (g2), the molecular weight or weight-average molecular weight of the components other than the energy-curable acrylic resin (g2-1) is preferably 100 to 50,000, and more preferably 300 to 20,000.

[0091] The acrylic polymer (g21) and the energy-curable compound (g22) constituting the energy-curable acrylic resin (g2-1) may each consist of only one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0092] ◎Acrylic polymer (g21) Examples of the functional groups in the acrylic polymer (g21) include hydroxyl groups, carboxyl groups, amino groups, substituted amino groups (groups having a structure in which one or two hydrogen atoms of an amino group are replaced by a group other than a hydrogen atom), epoxy groups, and the like.

[0093] Examples of acrylic polymers (g21) include acrylic polymers having a structure in which an acrylic monomer having the functional group and an acrylic monomer not having the functional group are copolymerized. In addition to these monomers, acrylic polymers may also have a structure in which monomers other than acrylic monomers (non-acrylic monomers) are copolymerized. The acrylic polymer (g21) may consist of only one acrylic monomer having the functional group, one acrylic monomer not having the functional group, and one non-acrylic monomer, and if there are two or more, their combinations and ratios can be arbitrarily selected.

[0094] Among the acrylic monomers having the aforementioned functional groups, examples of monomers containing hydroxyl groups include hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate; and non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols that do not have a (meth)acryloyl skeleton).

[0095] Examples of acrylic monomers that do not have the aforementioned functional groups include (meth)acrylic acid esters having aromatic groups, such as (meth)acrylic acid esters, in which the alkyl group constituting the alkyl ester has a chain structure with 1 to 18 carbon atoms, similar to the (meth)acrylic acid ester that constitutes the acrylic resin in the polymer component (a) described above; (meth)acrylic acid esters containing alkoxyalkyl groups such as methoxymethyl (meth)acrylic acid; and (meth)acrylic acid aryl esters such as phenyl (meth)acrylic acid.

[0096] Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

[0097] In the acrylic polymer (g21), the ratio (content) of the amount of constituent units derived from the functional group-containing acrylic monomer to the total amount of constituent units is preferably 1 to 50% by mass, for example, it may be any of 1 to 40% by mass, 1 to 35% by mass, and 1 to 30% by mass, or any of 10 to 50% by mass, 15 to 50% by mass, and 20 to 50% by mass, or any of 10 to 40% by mass, 15 to 35% by mass, and 20 to 30% by mass. By having the ratio within this range, in the energy-ray curable acrylic resin (g2-1), the content of energy-ray curable groups can be easily adjusted to a preferred range for the degree of curing of the energy-ray cured product (adhesive cured product) of the film-like adhesive.

[0098] ◎Energy ray curable compound (g22) The reactive group and the energy-ray-curable group of the energy-ray-curable compound (g22) may each be one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0099] The reactive group of the energy ray curable compound (g22) can be an isocyanate group, an epoxy group, a carboxyl group, etc., with an isocyanate group being preferred.

[0100] The energy-ray curable compound (g22) preferably has 1 to 5 of the energy-ray curable groups in one molecule, and more preferably 1 to 2.

[0101] Examples of energy-ray-curable compounds (g22) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0102] In the energy-ray curable acrylic resin (g2-1), the ratio of the content of the energy-ray curable group derived from the energy-ray curable compound (g22) to the content of the group derived from the functional group in the acrylic polymer (g21) is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and may be, for example, 50 to 100 mol%, 60 to 100 mol%, and 70 to 100 mol%. When the ratio is within this range, the adhesive strength of the energy-ray cured film adhesive is increased. Here, "the group derived from the functional group in the acrylic polymer (g21)" refers, for example, if the functional group is a hydroxyl group, to the "-O-" derived from the hydroxyl group after the hydroxyl group has reacted with the reactive group. Furthermore, if the energy-ray-curable compound (g22) has one of the reactive groups in one molecule, the upper limit of the ratio is 100 mol%, but if it has two or more of the reactive groups in one molecule, the upper limit of the ratio may exceed 100 mol%.

[0103] In a film-like adhesive, the ratio of the energy-ray curable component (g) to the total mass of the film-like adhesive is preferably 8 to 45% by mass, more preferably 10 to 40% by mass, for example, it may be any of 10 to 35% by mass, 10 to 28% by mass, and 10 to 22% by mass, or any of 13 to 40% by mass, 18 to 40% by mass, and 23 to 40% by mass, or any of 13 to 35% by mass and 18 to 28% by mass. When the ratio is above the lower limit, the effect obtained by using the energy-ray curable component (g) is increased. When the ratio is below the upper limit, it becomes easier to adjust the degree of the effect obtained by using components other than the energy-ray curable component (g). The aforementioned ratio is more preferable when the energy ray curable component (g) is an energy ray curable polymer (g2), and is particularly preferable when it is an energy ray curable acrylic resin (g2-1).

[0104] <Curing accelerator (c)> Curing accelerator (c) is a component for adjusting the thermal curing rate of the film-like adhesive. Preferred curing accelerators (c) include, for example, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are substituted with groups other than hydrogen atoms); tertiary amines; organophosphines (phosphines in which one or more hydrogen atoms are substituted with organic groups); tetraphenylborone salts; and inclusion compounds using the imidazoles as guest compounds.

[0105] When a curing accelerator (c) is used, the content of the curing accelerator (c) in composition (III) and the film adhesive is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the content of the thermosetting component (b) (for example, the total content of epoxy resin (b1) and thermosetting agent (b2)). When the content of the curing accelerator (c) is above the lower limit, the effect of using the curing accelerator (c) is more pronounced. When the content of the curing accelerator (c) is below the upper limit, for example, the effect of suppressing the migration and segregation of a highly polar curing accelerator (c) to the adhesive interface side with the adherend in the film adhesive under high temperature and high humidity conditions is enhanced, and the reliability of the package obtained using the film adhesive is further improved.

[0106] <Photopolymerization initiator (h)> The composition (III) and the film-like adhesive contain a photopolymerization initiator (h), which allows the polymerization (curing) reaction of the energy ray-curable component (g) to proceed efficiently.

[0107] Examples of the photopolymerization initiator (h) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene; 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; quinone compounds such as 1-chloroanthraquinone; and photosensitizers such as amines.

[0108] When a photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in composition (III) and the film adhesive is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7.5 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the energy ray curable component (g). When the content of the photopolymerization initiator (h) is above the lower limit, the effect obtained by using the photopolymerization initiator (h) is enhanced. When the content of the photopolymerization initiator (h) is below the upper limit, excessive use of the photopolymerization initiator (h) is suppressed.

[0109] <Other ingredients> Composition (III) and the film-like adhesive may contain, or may not contain, any other components that do not fall under any of the following categories: polymer component (a), thermosetting component (b), curing accelerator (c), energy ray curable component (g), or photopolymerization initiator (h). Examples of the other components mentioned above include fillers (d), coupling agents (e), crosslinking agents (f), colorants (i), and general-purpose additives (j). The other components contained in composition (III) and the film-like adhesive, such as fillers (d), coupling agents (e), crosslinking agents (f), colorants (i), and general-purpose additives (j), may consist of only one type or two or more types, and if there are two or more types, their combinations and ratios can be arbitrarily selected.

[0110] [Filler (d)] By using a film-like adhesive containing filler (d), it is possible to reduce the moisture absorption rate and improve the heat dissipation of the cured product, and furthermore, 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.

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

[0112] The filler (d) may be either an organic filler or an inorganic filler, but an inorganic filler is preferred. Preferred inorganic fillers include, for example, powders such as silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, and boron nitride; beads formed from these inorganic fillers in a spherical shape; surface-modified products of these inorganic fillers; single-crystal fibers of these inorganic fillers; and glass fibers. Among these, the inorganic filler is preferably silica, alumina, or a surface-modified version thereof.

[0113] In the film-like adhesive, the ratio of the filler (d) content to the total mass of the film-like adhesive is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the ratio is below the upper limit, as will be described later, the energy ray cured product (adhesive cured product) of the film-like adhesive can be cut more easily. On the other hand, the aforementioned ratio is 0% by mass or more. In terms of the ease of cutting the energy-ray cured product of the aforementioned film-like adhesive, it is most preferable that the ratio is 0% by mass, that is, that the film-like adhesive does not contain filler (d).

[0114] [Coupling agent (e)] The inclusion of coupling agent (e) in the film-like adhesive improves its adhesion and bonding to the substrate, and furthermore, the cured film-like adhesive exhibits improved water resistance without compromising its heat resistance. Coupling agent (e) has a functional group that can react with inorganic or organic compounds.

[0115] The coupling agent (e) is preferably a compound having a functional group that can react with the functional groups of the polymer component (a), the thermosetting component (b), etc., and is more preferably a silane coupling agent.

[0116] Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane (also known as 3-glycidoxypropyltrimethoxysilane; the same applies to other compounds hereafter), 3-glycidyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, imidazolesilane, oligomeric or polymeric organosiloxanes, and the like.

[0117] When using a coupling agent (e), the content of the coupling agent (e) in composition (III) and the film adhesive is preferably 0.03 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and may be, for example, 0.1 to 1 part by mass, based on 100 parts by mass of the total content of polymer component (a) and thermosetting component (b). When the content of the coupling agent (e) is above the lower limit, the effect obtained by using the coupling agent (e) is further enhanced. When the content of the coupling agent (e) is below the upper limit, the generation of outgassing is further suppressed.

[0118] [Crosslinking agent (f)] If polymer component (a) has the functional group that can bond with other compounds, such as the acrylic resin described above, the crosslinking agent (f) crosslinks the functional group in polymer component (a) with the other compound. In this case, the initial adhesive strength and cohesive strength of the film-like adhesive can be adjusted.

[0119] Examples of crosslinking agents (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).

[0120] In 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 polymer component (a). On the other hand, the content is 0 parts by mass or more. Since the pickability of the adhesive-cured chip tends to increase as the amount of crosslinking agent (f) decreases, it is particularly preferable that the amount is 0 parts by mass, that is, that the film-like adhesive does not contain crosslinking agent (f).

[0121] [Coloring agent (i)] The coloring agent (i) is a component in the film-like adhesive and its cured product that can adjust the transmittance of light of various wavelengths. Examples of colorants (i) include known ones such as inorganic pigments, organic pigments, and organic dyes.

[0122] When a coloring agent (i) is used, the ratio of the coloring agent (i) content to the total mass of the film adhesive is preferably 0.01 to 10% by mass, regardless of the type of coloring agent (i). When the ratio is above the lower limit, the effect of using the coloring agent (i) is more pronounced. When the ratio is below the upper limit, excessive use of the coloring agent (i) is suppressed.

[0123] [General-purpose additive (j)] The general-purpose additive (j) may be any known additive and can be arbitrarily selected depending on the purpose; it is not particularly limited. Preferred general-purpose additives (j) include, for example, plasticizers, antistatic agents, antioxidants, gettering agents, defoaming agents, leveling agents, and the like. The content of composition (III) and the general-purpose additive (i) in the film-like adhesive is not particularly limited and can be appropriately selected depending on the type of general-purpose additive (i), for example.

[0124] <Solvent> Composition (III) preferably further contains a solvent. Composition (III) containing a solvent has good handling properties. In this specification, unless otherwise specified, the term "solvent" includes not only substances that dissolve the target component but also dispersion media that disperse the target component.

[0125] 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 solvent contained in composition (III) may be one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0126] The solvent content of composition (III) is not particularly limited and may be appropriately selected depending on the type of components other than the solvent.

[0127] <<An example of a preferred film-type adhesive>> A preferred example of a film-like adhesive in this embodiment is a film-like adhesive having energy ray curability and thermosetting properties, The glass transition temperature Tg1 of the aforementioned film-like adhesive is 30°C or lower. The glass transition temperature Tg2 of the energy-ray cured product of the aforementioned film-like adhesive is 30°C or higher. The probe tack value t1 of the energy-ray cured film adhesive is 1.2 N / cm at 120°C. 2 That's all. A test piece measuring 25 mm in width and 150 mm in length is made of the aforementioned film-like adhesive and a test substrate made of low-density polyethylene with a thickness of 80 μm. This piece is attached to a silicon wafer using the film-like adhesive in the test piece at an attachment speed of 20 mm / s, an attachment pressure of 0.375 MPa, and an attachment temperature of 40°C. Next, a portion of the test substrate up to 50 mm from one end is peeled from the film-like adhesive, and a weight of 3.5 g is attached to the end of the peeled test substrate to create a test laminate. The test laminate is then fixed by holding the silicon wafer within the test laminate with the test substrate facing vertically downwards, and tension is applied to the test substrate from the weight. This state is maintained at room temperature for 24 hours. Then, the length L of the portion of the test substrate in the test laminate that has not been peeled from the film-like adhesive is measured. R A peel test is performed to measure the following formula (i) [Peel distance of test substrate] = 100 - L R (i) When the peeling distance of the test substrate is calculated by the above method, if the peeling distance is less than 100 mm, The aforementioned film-like adhesive contains a polymer component (a), a thermosetting component (b), and an energy ray curable component (g). In the aforementioned film-like adhesive, the ratio of the content of the polymer component (a) to the total mass of the film-like adhesive is 30% by mass or less. In the aforementioned film-like adhesive, the content of the thermosetting component (b) is 100 to 1000 parts by mass relative to the content of the polymer component (a) per 100 parts by mass. In the aforementioned film-like adhesive, the ratio of the content of the energy ray-curable component (g) to the total mass of the film-like adhesive is 8 to 45% by mass. The film-like adhesive either does not contain filler (d), or further contains filler (d), and in the case of the film-like adhesive containing filler (d), the ratio of the content of filler (d) to the total mass of the film-like adhesive is greater than 0% by mass and 15% by mass or less. However, in the film-like adhesive, the ratio of the total content of the polymer component (a), the thermosetting component (b), the energy ray curable component (g), and the filler (d) to the total mass of the film-like adhesive does not exceed 100% by mass. In a film-like adhesive containing such a polymer component (a), a thermosetting component (b), an energy ray curable component (g), and optionally a filler (d), the thermosetting component (b) is preferably an epoxy-based thermosetting resin consisting of an epoxy resin (b1) and a thermosetting agent (b2). In a film-like adhesive containing such an epoxy resin (b1) and a thermosetting agent (b2), the content of the thermosetting agent (b2) is preferably 1 to 10 parts by mass per 100 parts by mass of the epoxy resin (b1). Preferably, the probe tack integral value e1 at 120°C of the energy-ray cured film adhesive containing such polymer component (a), thermosetting component (b) (for example, epoxy resin (b1) and thermosetting agent (b2)), energy-ray curable component (g), and optionally filler (d) is 0.225 N·s or higher.

[0128] A more preferred example of a film-like adhesive in this embodiment is a film-like adhesive having energy ray curability and thermosetting properties, The glass transition temperature Tg1 of the aforementioned film-like adhesive is 30°C or lower. The glass transition temperature Tg2 of the energy-ray cured product of the aforementioned film-like adhesive is 30°C or higher. The probe tack value t1 of the energy-ray cured film adhesive is 1.2 N / cm at 120°C. 2 That's all. A test piece measuring 25 mm in width and 150 mm in length is made of the aforementioned film-like adhesive and a test substrate made of low-density polyethylene with a thickness of 80 μm. This piece is attached to a silicon wafer using the film-like adhesive in the test piece at an attachment speed of 20 mm / s, an attachment pressure of 0.375 MPa, and an attachment temperature of 40°C. Next, a portion of the test substrate up to 50 mm from one end is peeled from the film-like adhesive, and a weight of 3.5 g is attached to the end of the peeled test substrate to create a test laminate. The test laminate is then fixed by holding the silicon wafer within the test laminate with the test substrate facing vertically downwards, and tension is applied to the test substrate from the weight. This state is maintained at room temperature for 24 hours. Then, the length L of the portion of the test substrate in the test laminate that has not been peeled from the film-like adhesive is measured. R Measure and use the following formula (i) [Peel distance of test substrate] = 100 - L R (i) When the peeling distance of the test substrate is calculated by the above method, if the peeling distance is less than 100 mm, The aforementioned film-like adhesive contains a polymer component (a), a thermosetting component (b), a curing accelerator (c), an energy ray curing component (g), and a photopolymerization initiator (h). In the aforementioned film-like adhesive, the ratio of the content of the polymer component (a) to the total mass of the film-like adhesive is 30% by mass or less. In the aforementioned film-like adhesive, the content of the thermosetting component (b) is 100 to 1000 parts by mass relative to the content of the polymer component (a) per 100 parts by mass. In the aforementioned film-like adhesive, the ratio of the content of the energy ray-curable component (g) to the total mass of the film-like adhesive is 8 to 45% by mass. The film-like adhesive either does not contain filler (d), or further contains filler (d), and in the case of the film-like adhesive containing filler (d), the ratio of the content of filler (d) to the total mass of the film-like adhesive is greater than 0% by mass and 15% by mass or less. In the aforementioned film-like adhesive, the content of the curing accelerator (c) is 0.01 to 5 parts by mass per 100 parts by mass of the content of the thermosetting component (b). In the aforementioned film-like adhesive, the content of the photopolymerization initiator (h) is 0.1 to 10 parts by mass per 100 parts by mass of the energy ray curable component (g). However, in the film-like adhesive, the ratio of the total content of the polymer component (a), the thermosetting component (b), the curing accelerator (c), the energy ray curable component (g), the photopolymerization initiator (h), and the filler (d) to the total mass of the film-like adhesive does not exceed 100% by mass. In a film-like adhesive containing such a polymer component (a), a thermosetting component (b), a curing accelerator (c), an energy ray curable component (g), a photopolymerization initiator (h), and optionally a filler (d), the thermosetting component (b) is preferably an epoxy-based thermosetting resin consisting of an epoxy resin (b1) and a thermosetting agent (b2). In a film-like adhesive containing such an epoxy resin (b1) and a thermosetting agent (b2), the content of the thermosetting agent (b2) is preferably 1 to 10 parts by mass per 100 parts by mass of the epoxy resin (b1). The probe tack integral value e1 at 120°C of the energy-ray cured film adhesive containing such polymer component (a), thermosetting component (b) (e.g., epoxy resin (b1) and thermosetting agent (b2)), curing accelerator (c), energy-ray curable component (g), photopolymerization initiator (h), and optionally filler (d) is preferably 0.225 N·s or higher.

[0129] <<Method for manufacturing adhesive composition>> An adhesive composition (for example, composition (III)) is obtained by blending the components that constitute it. The temperature and time during the addition and mixing of each component are not particularly limited as long as the components do not deteriorate, and can be adjusted as appropriate, but a temperature of 15 to 30°C is preferred.

[0130] ◇Film-type adhesive composite sheet A film-like adhesive composite sheet according to one embodiment of the present invention comprises a base material and a film-like adhesive provided on one surface of the base material, wherein the film-like adhesive is the film-like adhesive according to the above-described embodiment of the present invention. Using the film-like adhesive composite sheet of this embodiment, multiple chips are held together on the exposed surface of the film-like adhesive within it, and the film-like adhesive is cured by energy rays to form a cured product. The substrate is then expanded under cooling conditions in a direction parallel to the side of the substrate where the cured product is located, thereby cutting the energy-ray cured film-like adhesive product and producing the chips with the cured adhesive product attached. Furthermore, by using the adhesive-cured chip, pressing the adhesive-cured material within it onto a circuit board, further heat-curing the adhesive-cured material, and connecting and fixing the chip to the circuit board, a circuit board device can be manufactured.

[0131] 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.

[0132] Figure 3 is a schematic cross-sectional view showing an example of a film-like adhesive composite sheet according to this embodiment. The film-like adhesive composite sheet 101 shown in Figure 3 comprises a base material 11 and a film-like adhesive 13 provided on one surface (sometimes referred to as the "first surface" in this specification) 11a of the base material 11. The film-like adhesive 13 is the film-like adhesive 13 shown in Figure 1.

[0133] In the film-like adhesive composite sheet 101, the first surface (one side) 13a of the film-like adhesive 13 is the side opposite to the substrate 11, and a ring frame adhesive layer 16 is provided in the region of the first surface 13a near the periphery of the film-like adhesive 13 (a region with an annular planar shape along the periphery).

[0134] The film-like adhesive composite sheet 101 further includes a release film 15 that is in contact with the first surface 13a of the film-like adhesive 13 and the exposed surface of the ring frame adhesive layer 16 on the side opposite to the film-like adhesive 13. In the film-like adhesive composite sheet 101, the release film 15 has any configuration.

[0135] The film-like adhesive composite sheet 101 is used with the release film 15 removed, and the chip is attached to the first surface 13a of the film-like adhesive 13. The exposed surface of the ring frame adhesive layer 16 is attached to the ring frame.

[0136] The other surface 11b of the base material 11 (which may be referred to as the "second surface" in this specification) is the outermost surface of the film-like adhesive composite sheet 101.

[0137] The film-like adhesive composite sheet of this embodiment is not limited to that shown in Figure 2, and for example, some components of this film-like adhesive composite sheet may be modified, deleted, or added without departing from the spirit of the present invention.

[0138] For example, the film-like adhesive composite sheet 101 may or may not have any other layers in any location that do not fall under any of the following categories: the base material 11, the film-like adhesive 13, the ring frame adhesive layer 16, or the release film 15.

[0139] Next, each layer constituting the film-like adhesive composite sheet of this embodiment will be described in more detail.

[0140] <<Base material>> The substrate may be in the form of a sheet or a film, and may be one of known types. As described later, in order to cure the film-like adhesive by irradiation with energy rays through the substrate, it is preferable that the substrate be one that is permeable to energy rays. Examples of constituent materials for the base material include various resins. The resin constituting the base material may consist of only one type, or two or more types. If there are two or more types, their combination and ratio can be arbitrarily selected.

[0141] Examples of the aforementioned resins include polyolefins such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and polypropylene; ethylene-based copolymers such as ethylene-vinyl acetate copolymer and ethylene-(meth)acrylic acid copolymer (polymers obtained using ethylene as a monomer); vinyl chloride resins (resins obtained using vinyl chloride as a monomer); polyester; and polyimide. The resin may be any of the following: a polymer alloy such as a mixture of two or more of the above-mentioned resins; a crosslinked resin obtained by crosslinking one or more of the above-mentioned resins; or a modified resin such as an ionomer using one or more of the above-mentioned resins.

[0142] In addition to the main constituent materials such as the aforementioned resin, the base material may also contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, plasticizers, and antistatic agents.

[0143] The surface of the substrate may or may not be treated with oxidation, lipophilicity, hydrophilicity, or primer treatment, and other layers may or may not be deposited on it.

[0144] The base material may consist of one layer (single layer) or of two or more layers. If it consists of multiple layers, these layers may be identical or different, and the combination of these layers is not particularly limited.

[0145] The thickness of the substrate is preferably 50 to 200 μm, more preferably 65 to 150 μm, and even more preferably 70 to 120 μm. A substrate thickness greater than or equal to the lower limit increases the strength of the substrate (film-like adhesive composite sheet). A substrate thickness greater than or equal to the lower limit also improves the flexibility of the film-like adhesive composite sheet and its suitability for adhesion to wafers.

[0146] The substrate can be manufactured by known methods. For example, a substrate containing a resin can be manufactured by molding a resin composition containing the resin.

[0147] <<Release film>> The aforementioned release film is the same as the first release film or second release film (first release film 151 or second release film 152 shown in Figure 1).

[0148] <<Adhesive layer for ring frame>> The adhesive layer for the ring frame may be a known type. The adhesive layer for the ring frame may be, for example, a single-layer structure containing adhesive components, or a multi-layer structure in which layers containing adhesive components are laminated on both sides of the core material sheet.

[0149] <<Other layers>> The aforementioned other layers (layers that do not fall under the categories of the base material, the film-like adhesive, the ring frame adhesive layer, or the release film) can be arbitrarily selected according to the purpose and are not particularly limited. In this embodiment, it is preferable that the film-like adhesive composite sheet does not have any of the aforementioned other layers between the film-like adhesive and the release film, between the film-like adhesive and the adhesive layer for the ring frame, and between the substrate and the film-like adhesive. By using such a film-like adhesive composite sheet, the effects of the present invention described above can be obtained more significantly.

[0150] <<Manufacturing method for film-like adhesive composite sheets>> The film-like adhesive composite sheet of this embodiment can be manufactured by laminating the above-mentioned layers in corresponding positional relationships and, if necessary, adjusting the shape of some or all of the layers. The method for forming each layer is as described above. The film-like adhesive composite sheet of this embodiment can be manufactured in the same way as a conventional film-like adhesive composite sheet, except that the film-like adhesive is used.

[0151] For example, when laminating a film-like adhesive onto a substrate, 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 substrate (the first or second side).

[0152] ◇Manufacturing method for substrate devices (Method of using film-type adhesive composite sheets) The aforementioned film-like adhesive composite sheet can be used to manufacture chips with cured adhesive, and the resulting chips with cured adhesive can be further used to manufacture substrate devices. A method for manufacturing a substrate device according to one embodiment of the present invention is a method for manufacturing a substrate device using the film-like adhesive composite sheet according to the above-described embodiment of the present invention, The aforementioned substrate device is configured such that the chip is connected to and fixed to the circuit board. In the above manufacturing method, a group of chips with a film-like adhesive composite sheet, comprising the film-like adhesive composite sheet and a plurality of chips held on the exposed surface of the film-like adhesive in the film-like adhesive composite sheet, is fixed to a ring frame via a ring frame adhesive layer at the peripheral edge of the film-like adhesive. In an atmosphere containing oxygen, the film-like adhesive in the chip group with the fixed film-like adhesive composite sheet is irradiated with energy rays through the substrate to produce an energy-ray cured product of the film-like adhesive. Under cooling conditions, after irradiation with the energy rays, the substrate is expanded in a direction parallel to the side of the substrate where the energy ray cured material is located, and the energy ray cured material is cut along the outer circumference of the tip, thereby producing a chip with an adhesive cured material, comprising the tip and the energy ray cured material of the film-like adhesive after cutting, which is provided on the back surface of the tip. The adhesive-cured chip is separated from the substrate and picked up, and the chip is pressed against the circuit board using the energy ray curing material to connect the chip in the adhesive-cured chip to the circuit board. The energy ray curing material is then further thermally cured to fix the chip to the circuit board.

[0153] The manufacturing method for the substrate device of this embodiment can be the same as that for conventional substrate devices, except that it uses the aforementioned film-like adhesive composite sheet.

[0154] The chip group with the film-like adhesive composite sheet can be manufactured by known methods. For example, grooves (e.g., multiple grooves in two mutually orthogonal directions) for forming chips of the desired size are formed on the circuit surface of a wafer before it is divided into chips. A backgrind tape is attached to the circuit surface of the wafer after these grooves have been formed. The back surface of the wafer is ground until the grooves are exposed and the wafer is divided into chips. The exposed surface of the film-like adhesive in a single film-like adhesive composite sheet (the first surface) is attached to the back surface (in other words, the ground surface) of the multiple chips formed in an aligned state, thereby fixing these multiple chips together on a single film-like adhesive composite sheet. The backgrind tape is then removed from the circuit surface of the chips (in other words, the surface that was the circuit surface of the wafer) to obtain the chip group with the film-like adhesive composite sheet.

[0155] In this embodiment, the chip group with a film-like adhesive composite sheet is used, in which the peripheral edge of the film-like adhesive within the chip is fixed to the ring frame via an adhesive layer for the ring frame. Examples of ring frames include those made of stainless steel.

[0156] In chip groups with film-like adhesive composite sheets, tension is typically applied to the film-like adhesive composite sheet in the width direction while it is fixed to a ring frame. Therefore, when using conventional film-like adhesive composite sheets, if the fixing time to the ring frame is extended to a long period, such as 24 hours or more, the width of the film-like adhesive composite sheet may shrink, causing a displacement in its position relative to the ring frame. Such displacement can lead to wrinkles or sagging in the film-like adhesive composite sheet, hindering the manufacturing of semiconductor devices. In contrast, in this embodiment, by using the film-like adhesive composite sheet according to the above-described embodiment, the occurrence of misalignment of the position of such film-like adhesive composite sheet relative to the ring frame is suppressed. This is because the peeling distance of the film-like adhesive becomes less than 100 mm. This characteristic is achieved by increasing the t1 of the energy ray cured product of the film-like adhesive.

[0157] In this embodiment, irradiating a film-like adhesive with energy rays through the substrate means irradiating the film-like adhesive composite sheet with energy rays from the outside of the second surface side of the substrate, thereby irradiating the film-like adhesive with energy rays that have passed through the substrate.

[0158] In this embodiment, the film-like adhesive is irradiated with energy rays through the substrate in an atmosphere of oxygen-containing gas. This method yields remarkable effects, as will be described later. The oxygen-containing gas is not particularly limited, but air is preferred.

[0159] In this embodiment, when curing the film-like adhesive with energy rays, the illuminance and light quantity of the energy rays are preferably within the numerical range described above.

[0160] By energy ray curing of a film-like adhesive, a group of chips with a cured composite sheet is obtained, comprising a substrate, an energy ray cured film-like adhesive provided on one surface (first surface) of the substrate, and a plurality of chips arranged in alignment on the surface of the energy ray cured film-like adhesive opposite to the substrate side.

[0161] The cooling temperature when expanding the substrate (in other words, when expanding the group of chips with a cured composite sheet in the width direction) is preferably -20 to 5°C, and more preferably -15 to 0°C. A cooling temperature above the lower limit makes it easier to suppress cracking of the substrate during expansion. A cooling temperature below the upper limit further improves the cutability of the energy-ray cured film-like adhesive. Here, the cooling temperature is synonymous with the cooling temperature of the energy ray-cured product when the substrate is expanded as described above after irradiation with energy rays, and is substantially the cooling temperature of the chip group with the cured composite sheet. Multiple adhesive-cured chips are fabricated on a substrate by cutting the energy-ray cured film-like adhesive.

[0162] By expanding the group of chips with cured composite sheets in the width direction, the energy-ray cured film adhesive is cleanly cut along the outer circumference of the chip. This is because, when the film adhesive is irradiated with energy rays, the film adhesive in the area attached to (in contact with) the chip hardens sufficiently, forming a highly hardened energy-ray cured product (adhesive cured product). The reason why the film adhesive hardens sufficiently in this area is presumed to be that the film adhesive is covered by the substrate and the chip, and even in an atmosphere of oxygen-containing gas, the film adhesive is not directly exposed to oxygen, thus maintaining its energy-ray curability. These properties of film-like adhesives are achieved by ensuring that the glass transition temperature Tg2 of the energy-ray cured film-like adhesive is 30°C or higher.

[0163] In contrast, in areas of the film adhesive that are not attached to the chip, energy ray curing of the film adhesive does not proceed sufficiently even when irradiated with energy rays. The reason for this is presumed to be that this area is directly exposed to oxygen in an atmosphere containing oxygen gas, which reduces the energy ray curability of the film adhesive. For this reason, the tackiness is moderately maintained in this area of ​​the energy ray cured film adhesive. Thus, the main areas of the cured material in which energy ray curing has not progressed sufficiently are the area near the periphery and the area exposed between adjacent chips. In particular, the area near the periphery of the cured material that is not involved in the formation of the adhesive-cured chip has moderate tackiness, which suppresses the scattering of the cured material in this area during expansion. These properties of film-like adhesives are achieved by having a glass transition temperature (Tg1) of 30°C or lower.

[0164] The picking of the adhesive-cured chip from the substrate and the pressing of the picked-up adhesive-cured chip onto the circuit board can each be performed by known methods.

[0165] It is preferable to press the adhesive-cured chip (in other words, the adhesive-cured material) onto the circuit board while heating it, and the heating temperature in this case is preferably 80 to 200°C, and more preferably 100 to 180°C. When the heating temperature is above the lower limit, the degree of adhesion between the adhesive-cured material and the circuit board is increased. When the heating temperature is below the upper limit, excessive heating is suppressed.

[0166] The pressure during crimping is preferably between 1 kPa and 200 MPa. A pressure above the lower limit enhances the effect of suppressing the formation of voids between the thermoset adhesive and the circuit board, as described later. A pressure below the upper limit suppresses damage to the adhesive-coated chip.

[0167] The pressing time is preferably 0.1 seconds to 5 minutes, and more preferably 0.5 seconds to 3 minutes. A pressing time above the lower limit enhances the effect of suppressing the formation of gaps between the thermoset adhesive and the circuit board, as described later. A pressing time below the upper limit prevents excessively long pressing times.

[0168] After the chip with the cured adhesive is pressed onto the circuit board, the chip is further fixed to the circuit board by thermal curing the adhesive to create a thermoset material. The thermoset adhesive has high impact resistance and maintains sufficient adhesion to the chip even under harsh high temperature and high humidity conditions.

[0169] The heating temperature during the thermal curing of the adhesive is preferably 100 to 180°C, more preferably 120 to 160°C, and even more preferably 130 to 150°C. A heating temperature above the lower limit facilitates the thermal curing of the adhesive. A heating temperature below the upper limit suppresses excessive heating.

[0170] The heating time during the thermal curing of the adhesive is preferably 15 to 120 minutes, more preferably 30 to 90 minutes, and even more preferably 30 to 60 minutes. A heating time above the lower limit results in a higher degree of thermal curing of the adhesive. A heating time below the upper limit prevents excessively long heating times.

[0171] Normally, when the adhesive-cured chip is pressed onto a circuit board, a gap is likely to form between the adhesive and the circuit board (air is easily trapped and remains). Furthermore, this gap is not eliminated even after the adhesive has heat-cured, and a gap is likely to remain between the heat-cured adhesive and the circuit board. In contrast, when using the film-like adhesive composite sheet of this embodiment, the probe tack value t1 of the energy-ray cured product of the film-like adhesive is 1.2 N / cm². 2As a result of the above, the size of the void between the cured adhesive and the circuit board can be reduced. Furthermore, after the heat curing of the adhesive, the void is eliminated, and the remaining void between the heat-cured adhesive and the circuit board can be suppressed.

[0172] In this embodiment, the desired substrate device can be obtained by the above steps, or by adding other steps as necessary. As described above, the substrate device obtained by this embodiment has high reliability because the remaining voids between the thermoset adhesive and the circuit board are suppressed. [Examples]

[0173] The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited in any way to the examples shown below.

[0174] <<Raw materials for resin manufacturing>> The full names of the resin manufacturing raw materials, which are abbreviated in this example and comparative example, are shown below. BA: n-butyl acrylate MA: Methyl acrylate MMA: Methyl methacrylate GMA: Glycidyl methacrylate HEA: 2-hydroxyethyl acrylate

[0175] <<Raw materials for manufacturing adhesive compositions>> The raw materials used in the manufacture 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, weight-average molecular weight 700,000) (a)-2: Acrylic resin obtained by copolymerizing BA (55 parts by mass), MA (10 parts by mass), GMA (20 parts by mass), and HEA (15 parts by mass) (weight-average molecular weight 900,000, glass transition temperature -28°C). [Epoxy resin (b1)] (b1)-1: Dicyclopentadiene type epoxy resin (XD-1000, manufactured by Nippon Kayaku Co., Ltd., softening point 68-78°C, epoxy equivalent 245-260 g / eq) (b1)-2: Mixture of liquid bisphenol F type epoxy resin and acrylic rubber fine particles (Nippon Shokubai Co., Ltd. "Acryset (registered trademark) BPF307", epoxy equivalent 235 g / eq) (b1)-3: Solid trishydroxyphenylmethane type epoxy resin (EPPN-502H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 167 g / eq, softening point 54°C, molecular weight 1200) (b1)-4: Mixture of liquid bisphenol A type epoxy resin and acrylic rubber fine particles (Acryset® BPA328, manufactured by Nippon Shokubai Co., Ltd., epoxy equivalent 235 g / eq) [Thermosetting agent (b2)] (b2)-1: Dicyandiamide (ADEKA Hardener® EH-3636AS, manufactured by ADEKA Corporation, solid dispersion latent curing agent, softening point 209°C, hydroxyl group equivalent 21 g / eq) (b2)-2: Novolac-type phenolic resin (Showa Denko Corporation's "Shounol® BRG-556", hydroxyl group equivalent 104 g / eq) [Curing accelerator (c)] (c)-1:2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemicals Co., Ltd. "Curesol (registered trademark) 2PHZ-PW") [Filler (d)] (d)-1: Spherical silica (Admatex "AdmaFine SC2050") [Coupling agent (e)] (e)-1:3-Glycidoxypropyltrimethoxysilane-added silicate compound ("MKC® Silicate MSEP-2" manufactured by Mitsubishi Chemical Corporation) [Energy ray curing component (g)] (g)-1: An acrylic copolymer obtained by copolymerizing BA (62 parts by mass), MMA (10 parts by mass), and HEA (28 parts by mass) is then reacted with 2-methacryloyloxyethyl isocyanate at an addition rate of 80 mol% relative to HEA to produce a resin ("Corponyl UN-2528LM1" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., weight-average molecular weight 30,000, solid content concentration 45% by mass) (g)-2: Tricyclodecanedimethylol diacrylate (manufactured by Nippon Kayaku Co., Ltd., "KAYARAD® R-684", molecular weight 304) [Photopolymerization initiator (h)] (h)-1:1-Hydroxycyclohexylphenyl ketone (BASF's "Irgacure® 184")

[0176] [Example 1] <<Manufacturing of film-type adhesives>> <Manufacturing of adhesive compositions> Adhesive compositions were prepared by dissolving or dispersing each component in methyl ethyl ketone and stirring at 23°C, so that the types and amounts of components contained in the film-like adhesive were as shown in Table 1, and the mixture was stirred to obtain an adhesive composition in which the total concentration of all components other than the solvent was 50% by mass. Note that the component content shown in Table 1 represents the content of the target product excluding the solvent.

[0177] <Manufacturing of film-type adhesives> A release film (second release film, Lintec Corporation's "SP-PET502150", 50 μm thick) made of polyethylene terephthalate film, in which one side was treated with a silicone-based release agent, was used. The adhesive composition obtained above was applied to the treated surface, and the film was dried at 100°C for 1 minute to produce a film-like adhesive (5 μm thick) that possesses both energy ray curability and thermosetting properties. Furthermore, by laminating the release-treated surface of a separate release film (first release film, Lintec Corporation's "SP-PET381031", 38 μm thick) to the exposed surface of the obtained film-like adhesive that does not have the second release film, a film-like adhesive with a release film was manufactured, comprising the film-like adhesive, the first release film provided on one side of the film-like adhesive, and the second release film provided on the other side of the film-like adhesive.

[0178] <<Manufacturing of film-like adhesive composite sheets>> <Manufacturing of base materials> A low-density polyethylene (LDPE) resin composition was extruded using a small T-die extruder (Laboplastmill, manufactured by Toyo Seiki Seisakusho Co., Ltd.) to produce a low-density polyethylene substrate (70 μm thick).

[0179] <Manufacturing of film-like adhesive composite sheets> The first release film was removed from the film-like adhesive obtained above, and one side of the substrate obtained above was bonded to the exposed surface of the film-like adhesive. This resulted in a composite sheet of film-like adhesive with a release film, in which the substrate, the film-like adhesive, and the second release film were laminated in this order in the thickness direction.

[0180] <<Manufacturing of silicone chips with cured adhesive>> <Fabrication of a group of silicon chips with a film-like adhesive composite sheet> Using a half-cut dicer (DISCO "DFG6363"), half-cuts were performed on a 12-inch silicon wafer, creating grooves at 8mm intervals in two mutually orthogonal directions, extending from the surface to a certain distance along its thickness. After half-cutting, a backgrind tape (Lintec Corporation's "Adwill E-3125KN") was applied to the grooved surface of the silicon wafer. Using a polishing device (DISCO Corporation's "DFG8761"), the back surface of the silicon wafer was ground, creating grooves on the ground surface. This allowed the silicon wafer to be divided at the grooved areas, and silicon chips (6mm x 6mm in size, 75μm thick) were fabricated.

[0181] In the film-like adhesive composite sheet obtained above, the second release film was removed at room temperature, and the exposed surface of the film-like adhesive was collectively attached to the back surface (grinding surface) of the group of silicon chips (silicon chip group) obtained above. At this time, the area near the periphery of the exposed surface of the film-like adhesive was further fixed to a stainless steel ring frame via a ring frame adhesive layer. Next, the backgrind tape was irradiated with ultraviolet light to cure the adhesive layer within the backgrind tape, and the backgrind tape was removed from the group of silicone chips. Based on the above, a group of silicon chips with a film-like adhesive composite sheet was fabricated, comprising a film-like adhesive composite sheet and a plurality of silicon chips aligned and held on the exposed surface of the film-like adhesive in the film-like adhesive composite sheet (the surface opposite to the substrate side).

[0182] <Manufacturing of silicone chips with cured adhesive> Next, under an air atmosphere, the film adhesive in the group of silicone chips with film adhesive composite sheets fixed to the ring frame was subjected to ultraviolet irradiation using a high-pressure mercury lamp equipped with an ultraviolet irradiation device (Lintec Corporation "RAD2010") at an illuminance of 230 mW / cm². 2 , light intensity 190mJ / cm 2 Under these conditions, a film-like adhesive was cured by UV irradiation through the substrate, and a group of silicone chips with a cured composite sheet was fabricated. Next, the resulting group of silicone chips with cured composite sheets was cooled at a temperature of -15°C, and the substrate was expanded in a direction parallel to the side surface of the UV-cured material, thereby cutting the UV-cured material along the outer circumference of the silicone chips. In this way, a large number of silicone chips with adhesive curing material, each comprising a silicone chip and the UV-cured film-like adhesive provided on the back surface of the silicone chip after cutting, were manufactured on the substrate, and a group of silicone chips with adhesive curing material was obtained.

[0183] <<Evaluation of film-type adhesives>> <Measurement of glass transition temperature Tg1 of film-like adhesives> Under an air atmosphere, the first and second release films were removed from the film-like adhesive obtained above. The storage modulus and loss tangent of this film-like adhesive were measured using a rheometer (Anton Paar "MCR301") to determine Tg1. The results are shown in Table 1.

[0184] <Measurement of the glass transition temperature (Tg2) of energy-ray cured film-type adhesives> From the film-like adhesive obtained above, the first and second release films are removed, and the film-like adhesive is subjected to ultraviolet irradiation at an illuminance of 230 mW / cm² in an air atmosphere using a UV irradiation device equipped with a high-pressure mercury lamp (Lintec Corporation "RAD2010"). 2 , light intensity 190mJ / cm 2 Under these conditions, the film-like adhesive was cured by irradiating it with ultraviolet light. The UV-cured film-like adhesive was subjected to a Tg2 measurement, similar to the procedure for the film-like adhesive described above. The results are shown in Table 1.

[0185] <Measurement of probe tack value t1 of energy-ray cured film-type adhesives> From the composite sheet with release film and adhesive obtained above, a 2cm x 2cm section was cut out and exposed to ultraviolet light in an air atmosphere at an illuminance of 230mW / cm² using the aforementioned ultraviolet irradiation device. 2, light intensity 190mJ / cm 2 Under these conditions, the film-like adhesive in the section was cured by irradiating it with ultraviolet light. Next, the second release film was peeled off from the UV-cured film-like adhesive, and the adhesive side of cellophane tape (manufactured by Nichiban Co., Ltd.) was attached to the exposed surface of the UV-cured material. The base material was then removed from the UV-cured material to obtain a laminate of cellophane tape and the UV-cured material.

[0186] Using a probe tack tester (TE-6002, manufactured by Tester Sangyo Co., Ltd.), the probe tack value of the exposed surface of the UV-cured material in the laminate, heated to 120°C, was measured, and the maximum value was determined. The measurement conditions for the probe tack value were as follows: A stainless steel probe with a diameter of 5 mm was used as the probe, and the probe tack value was 9.80665 N / cm² relative to the exposed surface of the UV-cured material. 2 (1000gf / cm 2 A load of ) was applied for 5 seconds. The probe's movement speed when pressing the probe against the laminate and when pulling it away from the laminate was set to 0.1 cm / s. Furthermore, all steps up to this point, from UV curing of the film-like adhesive to measurement of the probe tack value, were performed under an air atmosphere. These probe tack values ​​were measured at 10 different locations on the exposed surface, and the minimum of the 10 maximum values ​​obtained was adopted as the t1 of the UV-cured film adhesive. The results are shown in Table 1.

[0187] <Measurement of probe tack integral value e1 of energy-ray cured film-like adhesive> During the measurement of the probe tack value described above, the integral probe tack value was also measured simultaneously, and the minimum value among the 10 measurements obtained was adopted as e1 of the UV-cured film adhesive. The results are shown in Table 1.

[0188] <Measurement of peel distance of test substrate> The peeling test was conducted by the method described with reference to FIG. 2, and the peeling distance of the test substrate was measured. That is, in the same manner as in the production of the above film-like adhesive composite sheet, a substrate made of low-density polyethylene (thickness: 80 μm) was produced and used as the test substrate. The first peeling film was removed from the film-like adhesive obtained above, and one surface of the test substrate was bonded to the exposed surface of the film-like adhesive thus formed, thereby producing a laminate of the test substrate, the film-like adhesive, and the second peeling film. A section having a width of 25 mm and a length of 150 mm was produced from this laminate, and the second peeling film was removed to produce a test piece.

[0189] Using a tape mounter (Adwill RAD-2510F / 12 manufactured by Lintec Corporation), the test piece was bonded to one surface (grinding surface) of a silicon wafer (thickness: 350 μm) under the conditions of a bonding speed of 20 mm / s, a bonding pressure of 0.375 MPa, and a bonding temperature of 40°C by the film-like adhesive therein. Next, a portion of the test substrate after bonding from one end to 50 mm was peeled off from the film-like adhesive, and a weight of 3.5 g was attached to the end of the test substrate after peeling to produce a test laminate. Next, with the test substrate in the test laminate facing vertically downward and holding the silicon wafer in the test laminate, the test laminate was fixed, and tension from the weight against the test substrate was started and this state was maintained for 24 hours under a temperature condition of 23°C. And in the test substrate in the test laminate, L R was measured, and the peeling distance of the test substrate was calculated by the above formula (i). The results are shown in Table 1.

[0190] <Evaluation of the effect of suppressing the scattering of the energy ray-cured product of the film-like adhesive during expansion> After the production of the silicon chip with the above adhesive cured product, the region near the peripheral portion of the cured composite sheet was visually observed to confirm the presence or absence of scattering of the ultraviolet-cured product of the film-like adhesive. Then, the effect of suppressing the scattering of the ultraviolet-cured product was evaluated according to the following criteria. The results are shown in Table 1. [Evaluation Criteria] A: No UV-cured material from the film-type adhesive was scattered at all, demonstrating a scattering suppression effect. B: UV-cured film-type adhesive is scattering, and no effect in suppressing scattering has been observed.

[0191] <Evaluation of the cleavage properties of energy-ray cured film-type adhesives during expansion> Using a pickup die bonding device (Canon Machinery's "BESTEM D-510"), we attempted to pick up 25 silicone chips with adhesive curing material from the group of silicone chips with adhesive curing material obtained above, five chips each in the MD and TD directions of the film-like adhesive. The pickup was performed using five pickup pins, with a pickup height of 300 μm and a pickup speed of 10 mm / s. Based on the pickup results, the cleavageability of the UV-cured material was evaluated according to the following criteria. The results are shown in Table 1. If the energy-ray cured film-like adhesive is properly cut, adjacent silicone chips with adhesive curing material can be picked up normally without affecting each other. However, if the energy-ray cured film-like adhesive is not properly cut, they cannot be picked up normally. [Evaluation Criteria] A: All 25 silicone chips with cured adhesive were picked up successfully, and the UV-cured film adhesive was cut properly. B: There were silicone chips with cured adhesive that could not be picked up properly, and the UV-cured film adhesive was not cut properly.

[0192] <Evaluation of the effect of suppressing misalignment of the placement position of the film-like adhesive composite sheet relative to the ring frame> In the film-like adhesive composite sheet obtained above, the second release film was removed at room temperature, thereby exposing one side of the film-like adhesive. Using a tape mounter (Lintec "Adwill RAD-2510F / 12"), the exposed side of the film-like adhesive in the film-like adhesive composite sheet was attached to one side (ground surface) of a 12-inch silicon wafer (thickness 350 μm) under the conditions of attachment speed 20 mm / s, attachment pressure 0.375 MPa, and attachment temperature 40 °C. Based on the above, a silicon wafer with a film-like adhesive composite sheet was fabricated, comprising a film-like adhesive composite sheet and a silicon wafer provided on the exposed surface of the film-like adhesive within the film-like adhesive composite sheet (the surface opposite to the substrate side). Furthermore, the silicon wafer with the film-like adhesive composite sheet was fixed to a stainless steel ring frame via an adhesive layer for the ring frame at the peripheral edge of the film-like adhesive within it. The position of the film-like adhesive composite sheet relative to the ring frame was then recorded. For the adhesive layer used for the ring frame, a double-sided adhesive tape consisting of an acrylic adhesive and a polyolefin core material (Lintec Corporation's "G-01CPP-5MFF", 50 μm thick) was used.

[0193] After maintaining this fixed state for 24 hours under a temperature of 23°C, the position of the film-like adhesive composite sheet relative to the ring frame was recorded again. Then, the presence or absence of displacement of the film-like adhesive composite sheet during this 24-hour period was checked, and the effect of suppressing displacement was evaluated according to the following criteria. The results are shown in Table 1. [Evaluation Criteria] A: No displacement occurred in the placement position, and the effect of suppressing displacement was observed. B: There is a misalignment in the placement, and no effect in suppressing the misalignment is observed.

[0194] <Evaluation of the effect of the cured adhesive on suppressing the generation of voids between the thermoset material and the circuit board> In the same manner as when evaluating the cutability of the energy-ray cured material, ten silicon chips with adhesive curing material were selected from the group of silicon chips with adhesive curing material, and these silicon chips with adhesive curing material were die-bonded to the circuit board by pressing them onto the circuit board using the adhesive curing material (energy-ray cured material). This die bonding was performed by applying a force of 0.1 MPa for 1 second to the silicon chips with adhesive curing material heated to 120°C, in a direction perpendicular to the contact surface with the circuit board. At this stage, a scanning ultrasonic flaw detector (Hye-Focus, manufactured by Hitachi Construction Machinery FineTech Co., Ltd.) was used to check for the presence or absence of voids between the adhesive curing material and the circuit board in these ten silicon chips. The effect of suppressing the generation of voids between the adhesive curing material and the circuit board was then evaluated according to the following criteria. The results are shown in Table 1. [Evaluation Criteria] A: In all 10 silicon chips, there were no voids between the cured adhesive and the circuit board, demonstrating a high level of void formation suppression. B: In the case of 6 or more silicon chips, there are no voids between the cured adhesive and the circuit board, demonstrating an effect of suppressing void generation. C: There are five or fewer silicon chips with no voids between the cured adhesive and the circuit board, and the effect of suppressing void formation is not observed or is low.

[0195] Next, as described above, the effect of suppressing void formation was evaluated on the cured adhesive material. Then, the silicon chips were fixed to the circuit board by the cured adhesive material by heating the cured adhesive material at 150°C for 30 minutes and applying pressure of 0.5 MPa while simultaneously curing it. At this stage, the presence or absence of voids between the cured adhesive material and the circuit board was checked for 10 silicon chips, similar to the case with the cured adhesive material described above. The effect of suppressing void formation between the cured adhesive material and the circuit board was then evaluated according to the following criteria. The results are shown in Table 1. [Evaluation Criteria] A: In all 10 silicon chips, there were no voids between the thermosetting adhesive and the circuit board, demonstrating a high level of void formation suppression. B: In the case of 6 or more silicon chips, there are no voids between the thermoset product of the adhesive curing material and the circuit board, demonstrating an effect of suppressing void generation. C: There are five or fewer silicon chips with no voids between the thermoset adhesive and the circuit board, and the effect of suppressing void generation is not observed or is low.

[0196] <Package reliability evaluation> As described above, after evaluating the effect of suppressing void formation on the thermoset product of the adhesive curing material, a circuit board with 10 silicon chips fixed to it was dried by leaving it undisturbed for 20 hours under heating conditions of 120°C. Next, using a sealing device (GTM-S120T manufactured by Apic Yamada Co., Ltd.), the entire dried circuit board was covered with sealing resin (KE-1100AS3 manufactured by Kyocera Chemical Co., Ltd.), and the circuit board was sealed by heating it at 175°C while pressurizing it at a pressure of 7 MPa for 2 minutes, then releasing the pressure and heating it at 175°C for 5 hours. Next, a dicing sheet (Lintec Corporation's "Adwill D-510T") was attached to the encapsulated material, and using a dicing device (Disco Corporation's "DFD6362") and a blade (Disco Corporation's "ZHDG-SD400-D1-60 56×0.17A3×40-L-S356"), the dicing was performed at a dicing speed of 30 mm / s and a blade rotation speed of 30,000 rpm. The blade cut into the dicing sheet to a depth of 20 μm from the surface, dividing the encapsulated material into 15 mm × 15 mm pieces to create the packages. Next, using an ultraviolet irradiation device (Lintec Corporation's "RAD-2000"), an illuminance of 220 mW / cm² was applied. 2 , light intensity 200mJ / cm 2 After irradiating the dicing sheet with ultraviolet light under these conditions, 10 packages were picked from the dicing sheet and dried by leaving them undisturbed for 20 hours under heating conditions of 125°C.

[0197] Next, the 10 packages after drying were subjected to damp heat treatment at a temperature of 85°C and a relative humidity of 60% for 168 hours, and then IR reflow was performed 3 times using a reflow apparatus ("STR-2010M" manufactured by Senju Metal Industry Co., Ltd.) under the conditions of a heating temperature of 260°C and a heating time of 10 seconds. Next, using the scanning ultrasonic flaw detector, the presence or absence of cracks (damage) was confirmed in the 10 packages after IR reflow. And the package reliability was evaluated according to the following criteria. The results are shown in Table 1. [Evaluation Criteria] A: In all 10 packages, there are no cracks and the package reliability is high. B: In 6 or more packages, there are no cracks and the package reliability is good. C: The number of packages without cracks is 5 or less, and the package reliability is low.

[0198] <Manufacture of Film状 Adhesive, Manufacture of Film状 Adhesive Composite Sheet, and Evaluation of Film状 Adhesive>> [Examples 2 to 5, Comparative Example 1, Comparative Example 3] The film状 adhesive was manufactured in the same manner as in Example 1, except that only the blending amounts of the blending components of the adhesive composition, or the types and blending amounts of the blending components, were changed. The types and contents of the components of these film状 adhesives are shown in Tables 1 to 2. In addition, the description "-" in the column of the components of the film状 adhesive means that the film状 adhesive does not contain that component.

[0199] Furthermore, the film状 adhesive composite sheet was manufactured and the film状 adhesive was evaluated in the same manner as in Example 1, except that these film状 adhesives were used. The results are shown in Tables 1 to 2.

[0200] In the column of "Manufacturing Conditions" in Tables 1 to 2, the description "+" means that the operation is being performed, and the description "-" means that the operation is not being performed.

[0201] [Reference Example 1] In Example 5, the UV-cured film-like adhesive was cut using a group of silicone chips with a cured composite sheet. However, in this reference example, the film-like adhesive was not UV-cured, and the film-like adhesive was cut by expanding the substrate using a group of silicone chips with a film-like adhesive composite sheet. That is, in this reference example, except that the film-like adhesive was not UV-cured, a number of silicone chips with film-like adhesive were manufactured on a substrate, each consisting of a silicone chip and the cut film-like adhesive provided on the back surface of the silicone chip, similar to Example 5, to obtain a group of silicone chips with film-like adhesive. The effect of suppressing the scattering of the film-like adhesive and the cutting performance were evaluated in the same way as in the case of the UV-cured film-like adhesive described above. The results are shown in Table 2.

[0202] [Comparative Example 2] A group of silicone chips with adhesive-cured material was obtained in the same manner as in Comparative Example 1, except that the UV curing of the film-like adhesive was performed under a nitrogen gas atmosphere instead of an air atmosphere during the manufacturing of the adhesive-cured silicone chips. The effect of suppressing the scattering of the UV-cured film-like adhesive and the cleavage performance were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0203] [Table 1]

[0204] [Table 2]

[0205] As is clear from the results above, in Examples 1 to 5, the displacement of the film-like adhesive composite sheet relative to the ring frame was suppressed. In Examples 1 to 5, the peeling distance of the test substrate was 10 mm or less. Furthermore, in Examples 1 to 5, the remaining voids between the thermoset adhesive and the circuit board were suppressed, and the voids were eliminated, unlike before the thermosetting of the adhesive, resulting in good package reliability. In Examples 1-5, the t1 of the UV-cured film adhesive was 1.27 N / cm². 2 That was all.

[0206] Furthermore, in Examples 1 to 5, the UV-cured film adhesive could be sufficiently cut during expansion in an air atmosphere, and scattering of the cured material in the vicinity of its periphery was suppressed. In Examples 1 to 5, the Tg2 of the UV-cured film adhesive was 32°C or higher, and the Tg1 of the film adhesive was 27°C or lower.

[0207] In contrast, in Comparative Example 1, the displacement of the film-like adhesive composite sheet relative to the ring frame was not suppressed. In Comparative Example 1, the peeling distance of the test substrate was 100 mm. Furthermore, in Comparative Example 1, the retention of voids between the thermoset adhesive and the circuit board was not suppressed, and the voids remained even before the thermosetting of the adhesive, resulting in poor package reliability. In Comparative Example 1, the t1 of the UV-cured film-like adhesive was 1.18 N / cm². 2 That was the case.

[0208] In Comparative Example 3, the composition of the film-like adhesive differed from that of Examples 1-5 and Comparative Example 1. Furthermore, Comparative Example 3 differed from Examples 1-5 and Comparative Example 1 in that the film-like adhesive was not UV-cured, and a film-like adhesive-coated silicone chip was manufactured instead of a silicone chip with a cured adhesive. In Comparative Example 3, scattering of the film-like adhesive in the area near its periphery was not suppressed during expansion in an air atmosphere. In Comparative Example 3, the Tg1 of the film-like adhesive was 40°C.

[0209] Furthermore, the UV cured product e1 of the film-like adhesive was 0.235 N·s or higher in Examples 1 to 5, and 0.216 N·s or lower in Comparative Examples 1 and 3. Among these examples and comparative examples, e1 showed a similar trend to t1.

[0210] On the other hand, the film-like adhesive in Reference Example 1 was the same as the film-like adhesive in Example 5, but Reference Example 1 differed from Example 5 in that it manufactured silicone chips with film-like adhesive instead of silicone chips with cured adhesive by not curing the film-like adhesive with ultraviolet light. In Reference Example 1, the film-like adhesive exhibited poor cleavage during expansion in an air atmosphere. In Reference Example 1, the film-like adhesive could not be cut sufficiently, so no further evaluation was performed.

[0211] The film-like adhesive in Comparative Example 2 was the same as the film-like adhesive in Comparative Example 1, but the difference in Comparative Example 2 was that the UV curing of the film-like adhesive was performed in a nitrogen gas atmosphere instead of an air atmosphere. In Comparative Example 2, when expanding in a nitrogen gas atmosphere, scattering of the UV-cured film-like adhesive in the area near its periphery could not be suppressed. In Comparative Example 2, the UV-cured film-like adhesive could not be adequately cut, so no further evaluation was performed. In Comparative Example 2, the film-like adhesive was irradiated with ultraviolet light under a nitrogen gas atmosphere. Therefore, it was presumed that the region near the periphery of the film-like adhesive was not affected by oxygen in the air, resulting in a higher degree of curing. [Industrial applicability]

[0212] This invention can be used in the manufacture of substrate devices. [Explanation of symbols]

[0213] 11...Substrate, 11a...One side of the substrate (first side) 13...Film-type adhesive, 13a...One side (first side) of the film-type adhesive, 16...Adhesive layer for ring frame 101...Film-type adhesive composite sheet 6. Test laminate 7... weight 8. Test substrate 9. Silicon wafers 30... Test specimens L 30 ...length of the test piece L R ...Length of the portion of the test substrate that has not peeled off from the film-like adhesive.

Claims

1. A film-like adhesive having energy ray curing and thermosetting properties, Glass transition temperature Tg of the aforementioned film-like adhesive １ The temperature is below 30°C. Glass transition temperature Tg of the energy-ray cured product of the aforementioned film-like adhesive ２ The temperature is 30°C or higher. The probe tack value t of the energy-ray cured film adhesive at 120°C １ 1.2 N / cm ２ That's all. A test piece measuring 25 mm in width and 150 mm in length is made of the aforementioned film-like adhesive and a test substrate made of low-density polyethylene with a thickness of 80 μm. This test piece is attached to a silicon wafer using the film-like adhesive in the test piece at an attachment speed of 20 mm / s, an attachment pressure of 0.375 MPa, and an attachment temperature of 40°C. Next, a portion of the test substrate from one end up to 50 mm from the film-like adhesive is peeled off, and a weight of 3.5 g is attached to the end of the peeled test substrate to create a test laminate. The test laminate is then fixed by holding the silicon wafer within the test laminate with the test substrate facing vertically downwards, and tension is started on the test substrate from the weight. This state is maintained at room temperature for 24 hours. Then, the length L of the portion of the test substrate in the test laminate that has not been peeled off from the film-like adhesive is measured. Ｒ A peel test is performed to measure the following formula (i) [Peeling distance of test substrate] = 100 - L Ｒ (i) A film-like adhesive in which, when the peeling distance of the test substrate is calculated by the method described above, the peeling distance is less than 100 mm.

2. The probe tack integral value e at 120°C of the energy ray cured film-like adhesive. １ The film-like adhesive according to claim 1, wherein the coefficient of force is 0.225 N·s or more.

3. The invention comprises a base material and a film-like adhesive provided on one surface of the base material, A film-like adhesive composite sheet wherein the film-like adhesive is the film-like adhesive described in claim 1 or 2.

4. A method for manufacturing a substrate device using the film-like adhesive composite sheet described in claim 3, The aforementioned substrate device is configured such that the chip is connected to and fixed to the circuit board. In the above manufacturing method, a group of chips with a film-like adhesive composite sheet, comprising the film-like adhesive composite sheet and a plurality of chips held on the exposed surface of the film-like adhesive in the film-like adhesive composite sheet, is fixed to a ring frame via a ring frame adhesive layer at the peripheral edge of the film-like adhesive. In an atmosphere containing oxygen, the film-like adhesive in the chip group with the fixed film-like adhesive composite sheet is irradiated with energy rays through the substrate to produce an energy-ray cured product of the film-like adhesive. Under cooling conditions, after irradiation with the energy rays, the substrate is expanded in a direction parallel to the side of the substrate where the energy ray cured material is located, and the energy ray cured material is cut along the outer circumference of the tip, thereby producing a chip with an adhesive cured material, comprising the tip and the energy ray cured material of the film-like adhesive after cutting, which is provided on the back surface of the tip. A method for manufacturing a substrate device, comprising: pulling the adhesive-cured chip away from the substrate and picking it up; pressing the chip onto the circuit board using the energy ray curing material to connect the chip in the adhesive-cured chip to the circuit board; and further thermally curing the energy ray curing material after connection to fix the chip to the circuit board.

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