Method for manufacturing film-like adhesives, film-like adhesive composite sheets, and chips with cured adhesives.

Abstract

To provide a film-like adhesive that allows for the normal pickup of an adhesive-cured chip from a support sheet, obtained by cutting the film-like adhesive by plasma irradiation and curing it with energy rays. [Solution] A film-like adhesive for cutting by plasma irradiation, wherein the film-like adhesive is energy ray curable and has a tack reduction rate X of 0.12 or more. X = (Tb - Ta) / Tb. Tb is the probe tack value at 23°C after irradiating the film-like adhesive with plasma. Ta is the probe tack value at 23°C after irradiating the film-like adhesive with plasma and then with ultraviolet light.

Description

[Technical Field]

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

[0002] In the manufacturing of semiconductor devices, for example, a semiconductor chip with a film-like adhesive is manufactured, which comprises a semiconductor chip and a film-like adhesive provided on the back surface (the side opposite to the circuit surface) of the semiconductor chip. This film-like adhesive is then bonded and fixed to a circuit board using the film-like adhesive, and mounted. The film-like adhesive is usually thermosetting, meaning it hardens when heated. After bonding the semiconductor chip with the film-like adhesive to the circuit board, the film-like adhesive is heat-cured to fix the semiconductor chip to the circuit board.

[0003] The aforementioned film-like adhesive-coated semiconductor chip can be manufactured, for example, by the following method. Specifically, first, one film-like adhesive composite sheet (for example, a die bonding sheet) is used, which comprises a support sheet and a film-like adhesive provided on one side of the support sheet, and the film-like adhesive within it is attached to the back side (the side opposite to the circuit side) of the semiconductor wafer. Next, on the support sheet, the semiconductor wafer is divided to produce semiconductor chips, and the film-like adhesive is cut, thereby producing multiple semiconductor chips with the film-like adhesive on the support sheet. The division of the semiconductor wafer and the cutting of the film-like adhesive can be performed continuously by blade dicing or the like using a blade.

[0004] These film-like adhesive semiconductor chips are pulled away from the support sheet and picked up to obtain the desired film-like adhesive semiconductor chip. To facilitate this pick-up, the film-like adhesive may also have energy-ray curing properties in addition to the thermosetting properties described above, allowing it to harden when irradiated with energy rays such as ultraviolet light. By energy-ray curing the film-like adhesive before pick-up, the peeling force between the energy-ray cured film-like adhesive and the support sheet is reduced within an appropriate range, regardless of the type of support sheet, so that the semiconductor chip equipped with the cured material (adhesive-cured semiconductor chip) can be easily picked up from the support sheet (see Patent Document 1). Such energy-ray cured film-like adhesives can still be used as film-like adhesives. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2013-194103 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] On the other hand, the splitting of semiconductor wafers and the cutting of film-like adhesives can be performed continuously not only by blade dicing as described above, but also by plasma irradiation. However, in that case, even though the film-like adhesive is ultimately cured by energy rays, it becomes difficult to peel the energy-ray cured film-like adhesive from the support sheet, and conversely, it can become difficult to pick up the semiconductor chip with the cured adhesive attached from the support sheet.

[0007] The present invention aims to provide a film-like adhesive that enables the normal pickup of an adhesive-cured chip from a support sheet, obtained by cutting the film-like adhesive by plasma irradiation and curing it with energy rays. [Means for solving the problem]

[0008] To solve the above problems, the present invention employs the following configuration. [1] A film-like adhesive for cutting by plasma irradiation, wherein the film-like adhesive is energy ray curable and has a tack reduction rate X of 0.12 or more; The aforementioned tack reduction rate X is a value expressed by the following formula (1): X = (Tb - Ta) / Tb (1) Tb is the probe tack value at 23°C after performing the operation of irradiating the film-like adhesive with plasma for 1 minute 15 times under the conditions of gas species O2, flow rate 100 mL / min, and output 300 W. Ta performed the procedure of irradiating the film-like adhesive with plasma 15 times for 1 minute under the conditions of gas species O2, flow rate 100 mL / min, and output 300 W, and then, under a nitrogen gas atmosphere, with an irradiance of 220 mW / cm². 2 , light intensity 190mJ / cm 2 This is the probe tack value at 23°C after irradiation with ultraviolet light under the specified conditions. [2] The film-like adhesive according to [1], wherein the film-like adhesive contains an energy ray curable component (g) and a photopolymerization initiator (h). [3] The film-like adhesive according to [1] or [2], wherein energy rays are irradiated after the plasma has been irradiated. [4] The film-like adhesive according to [1] or [2], wherein the ratio of the content of antioxidant (j1) to the total mass of the film-like adhesive is 0.1 to 5% by mass. [5] A film-like adhesive composite sheet comprising a support sheet and a film-like adhesive provided on one surface of the support sheet, wherein the film-like adhesive is the film-like adhesive described in [1]. [6] The film-like adhesive composite sheet according to [5], wherein the support sheet consists only of a base material. [7] The illuminance for the film-like adhesive composite sheet is 230 mW / cm². 2 , light intensity 190mJ / cm 2 A test specimen (T3) with a width of 25 mm was prepared by irradiating the film-like adhesive with ultraviolet light under the specified conditions to cure it with ultraviolet light. In the test specimen (T3), the support sheet is peeled off from the UV-cured film-like adhesive, and the angle between the surface of the UV-cured film to which the support sheet was attached and the surface of the support sheet to which the UV-cured film was attached is set to 180°. When a peel test is performed in which the support sheet is peeled off from the UV-cured film-like adhesive in its longitudinal direction at a peel speed of 300 mm / min, the peel force between the UV-cured film-like adhesive and the support sheet is 100 mN / 25 mm or less, as described in [5] or [6]. A method for manufacturing a chip with an adhesive cured product using the film-like adhesive composite sheet described in [8] [5] or [6], The aforementioned adhesive-cured tip comprises a tip and an energy-ray cured film-like adhesive provided on one side of the tip. The manufacturing method for producing a chip with an adhesive-cured material, comprising: attaching the film-like adhesive in the film-like adhesive composite sheet to one side of a wafer; irradiating the wafer and the film-like adhesive with plasma to divide the wafer and produce a chip; cutting the film-like adhesive; and curing the cut film-like adhesive with energy rays to produce a chip with an adhesive-cured material; and then pulling the chip with the adhesive-cured material away from the support sheet and picking it up. [Effects of the Invention]

[0009] According to the present invention, a film-like adhesive is provided that enables the normal pickup of an adhesive-cured chip from a support sheet, obtained by cutting the film-like adhesive by plasma irradiation and curing it with energy rays. [Brief explanation of the drawing]

[0010] [Figure 1] A cross-sectional view schematically showing an example of a film-like adhesive according to an embodiment of the present invention. [Figure 2] A cross-sectional view schematically showing an example of a film-like adhesive composite sheet according to an embodiment of the present invention.

Mode for Carrying Out the Invention

[0011] ◇Film-like adhesive The film-like adhesive according to an embodiment of the present invention is a film-like adhesive for cutting by plasma irradiation, and the film-like adhesive has energy ray curability. The tack reduction rate of the film-like adhesive is 0.12 or more. When this tack reduction rate is referred to as the tack reduction rate X, although details will be described later, the tack reduction rate X is a value represented by the following formula (1). X = (Tb - Ta) / Tb (1) Tb is the probe tack value after plasma irradiation. Ta is the probe tack value after plasma and ultraviolet ray irradiation.

[0012] An adhesive-cured chip including a chip and an energy ray cured product of the film-like adhesive provided on one surface of the chip is used in the manufacture of a substrate device described later. The adhesive-cured chip is obtained by irradiating a film-like adhesive wafer including a wafer and the film-like adhesive provided on one surface of the wafer with plasma, dividing the wafer on a support sheet described later, cutting the film-like adhesive, and curing the cut film-like adhesive with energy rays. It can be manufactured by separating the adhesive-cured chip from the support sheet and picking it up.

[0013] That is, it is preferable that the film-like adhesive is for irradiating energy rays after being irradiated with plasma.

[0014] Because the tack reduction rate of the film-type adhesive is 0.12 or higher, peeling of the energy-ray cured film-type adhesive (adhesive cured product) from the support sheet is not difficult, and the adhesive-cured chip can be picked up normally from the support sheet.

[0015] 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.

[0016] 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 these wafers is the circuit side, on which the circuit is formed, and the side opposite to this is referred to in this specification as the "back side". The same applies to chips manufactured by dividing a wafer through methods such as dicing; the side of the chip opposite the circuit side on which the circuit is formed is called 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.

[0017] In this specification, "substrate device" means a device constructed by bonding and fixing an adhesive-cured chip to a circuit board using the adhesive. For example, if a semiconductor wafer is used as the workpiece, a semiconductor device can be considered a substrate device.

[0018] The film-like adhesive of this embodiment can be laminated with a support sheet to form a film-like adhesive composite sheet, which will be described later. This film-like adhesive composite sheet can be used in the same way as known dicing die bonding sheets.

[0019] The film-like adhesive of this embodiment may or may not have energy ray curability and thermosetting properties, but it is preferable that it has both energy ray curability and thermosetting properties. In the manufacturing process of a substrate device, the adhesive-cured chip can be mounted on the circuit board by adhering it to the circuit board with the adhesive curing material contained within it. Furthermore, if the adhesive curing material (energy ray curing material of the film-like adhesive) has thermosetting properties, the energy rays and thermosetting material formed by thermally curing the adhesive curing material after adhesion have high impact resistance and maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

[0020] In this specification, "energy ray" means an electromagnetic wave or charged particle beam that has an energy quantum. Examples of energy rays include ultraviolet rays, radiation, electron beams, etc. In this specification, "energy ray curable" means the property of hardening when irradiated with energy rays, and "non-energy ray curable" means the property of not hardening even when irradiated with energy rays. In this specification, "thermosetting" means the property of hardening upon heating.

[0021] When the cured product of the aforementioned film-like adhesive is actually used, the curing conditions for curing the film-like adhesive to form the cured product are not particularly limited, as long as the degree of curing of the cured product is sufficiently high, and can be appropriately selected according to the type of film-like adhesive. During the energy ray curing of film-type adhesives, the illuminance of the energy rays is 60-320 mW / cm². 2 Preferably, the amount of light from the energy ray during the energy ray curing process is 100 to 1000 mJ / cm². 2 It is preferable that this be the case. The heating temperature during the thermal curing of the adhesive cured product and the film-like adhesive is preferably 100 to 200°C. The heating time during the thermal curing is preferably 0.5 to 5 hours.

[0022] The film-like adhesive of this embodiment, which has energy ray curing properties, preferably contains an energy ray curing component (g), and more preferably contains an energy ray curing component (g) and a photopolymerization initiator (h). The film-like adhesive of this embodiment preferably contains polymer component (a) because it has good film-forming properties. In this embodiment, the film-like adhesive preferably contains an antioxidant (j1) in that it improves the pickability of the adhesive-cured chip. The components of the film-like adhesive in this embodiment will be described in detail later.

[0023] In this specification, the ability to properly pick up an object, such as a chip with cured adhesive, from a support sheet is sometimes referred to as "pickup capability."

[0024] <Tack reduction rate of film-type adhesives> The tack reduction rate (sometimes referred to as tack reduction rate X) of the aforementioned film-like adhesive is 0.12 or higher. In contrast, unlike this embodiment, when a film-like adhesive composite sheet is constructed using a conventional film-like adhesive with a tack reduction rate of less than 0.12, and adhesive-cured chips are manufactured, the adhesive-cured chips often cannot be properly picked up from the support sheet. The reason for this is not clear, but it is presumed to be as follows.

[0025] In other words, when a conventional film-like adhesive composite sheet, which is a laminate of a conventional film-like adhesive and a support sheet, is irradiated with plasma in an oxygen gas atmosphere to cut the film-like adhesive, radicals are generated from the decomposition products of the film-like adhesive and the oxygen gas. It is presumed that in the vicinity of the plasma-cut surface, the film-like adhesive and the support sheet deform, harden, and interlock in a minute area. In this specification, this phenomenon is referred to as "anchoring." Therefore, it is presumed that even if the film-like adhesive is cured by energy rays, the pickup of the adhesive-cured chip from the support sheet is inhibited. It is presumed that when a film-type adhesive with a tack reduction rate of 0.12 or higher is used, the curing reaction due to irradiation with energy rays such as ultraviolet light proceeds more easily than when a film-type adhesive with a tack reduction rate of less than 0.12 is used, and anchoring is more easily resolved by curing shrinkage due to the curing reaction, making it possible to normally pick up the adhesive-cured chip from the support sheet.

[0026] In terms of obtaining the above-mentioned effects of the present invention more significantly, a higher tack reduction rate of the film-like adhesive is preferable, and may be any of the following: 0.13 or higher, 0.15 or higher, 0.17 or higher, 0.19 or higher, 0.20 or higher, 0.25 or higher, 0.30 or higher, 0.35 or higher, or 0.40 or higher. When the tack reduction rate is above the aforementioned lower limit, anchoring is more easily resolved, making it easier to pick up the adhesive-cured chip from the support sheet. There is no particular upper limit to the tack reduction rate; for example, it may be 0.8 or less, or 0.6 or less.

[0027] The aforementioned tack reduction rate X is a value expressed by the following formula (1). X = (Tb - Ta) / Tb (1) Tb is the probe tack value of the film-like adhesive at 23°C after performing the operation of irradiating the film-like adhesive with plasma for 1 minute for 15 times under the conditions of gas species O2, flow rate 100 mL / min, and output 300 W. Ta is the probe tack value of the film adhesive at 23°C after irradiating the film adhesive with plasma 15 times for 1 minute under the conditions of gas species O2, flow rate 100 mL / min, and output 300 W, and then irradiating with ultraviolet light under a nitrogen gas atmosphere at an illuminance of 220 mW / cm 2 and a light quantity of 190 mJ / cm 2 .

[0028] The probe tack values Ta and Tb can be measured by known methods. For example, by the method shown below, the probe tack value of the film adhesive can be accurately measured, and the tack reduction rate can be calculated. That is, the film adhesive is cut into a size of 10 mm × 10 mm to obtain a test sample. Under an environment of 23°C and 50% RH (relative humidity), a stainless steel probe with a diameter of 5 mm is brought into contact with the surface of the test sample at a speed of 0.1 cm / s for 1 second with a contact load of 1000 gf / cm 2 (that is, 9.81 N / cm 2 ), and then the force required to separate the probe from the surface of the test sample at a speed of 0.1 cm / s is measured, and the obtained value is taken as the probe tack value of the test sample. As a measuring device, for example, a tacking tester (manufactured by Nippon Special Measuring Instruments Co., Ltd., product name "NTS-4800") can be used.

[0029] The probe tack value Tb of the film adhesive is preferably 50 to 300 mN, more preferably 80 to 200 mN, and still more preferably 1 to 50 mN. When the tack value Tb is at or above the lower limit value, it becomes easier to suppress peeling at the interface between the chip and the film adhesive at the stage before energy ray curing of the film adhesive in the manufacturing process of the chip with the adhesive cured product. By keeping the tack value Tb below the upper limit, contamination of the chip by contaminants originating from the film adhesive is more easily suppressed in the manufacturing process of adhesive-cured chips, before the film adhesive is cured by energy rays.

[0030] The probe tack value Ta of the film-like adhesive is preferably 30 to 100 mN, more preferably 40 to 90 mN, and even more preferably 50 to 80 mN. By having a tack value Ta equal to or greater than the aforementioned lower limit, it becomes easier to prevent the adhesive-cured silicon chip from unintentionally detaching from the support sheet in the manufacturing process of adhesive-cured chips, after the film-like adhesive has been cured by energy rays. When the tack value Ta is below the upper limit, the silicone chip with the cured adhesive can be easily picked up from the support sheet in the manufacturing process of the adhesive-cured chip, after the film adhesive has been cured by energy rays.

[0031] The probe tack value T0 is the probe tack value of the film-like adhesive at 23°C. The probe tack value T0 of the film-like adhesive is preferably 50 to 500 mN, more preferably 80 to 300 mN, and even more preferably 100 to 200 mN. When the tack value T0 is equal to or greater than the lower limit, it becomes easier to improve the adhesion of the film-like adhesive to the wafer.

[0032] The tack reduction rate of a film-type adhesive can be adjusted by controlling the type or amount of components it contains. In particular, the tack reduction rate of a film-type adhesive can be more easily controlled by adjusting the type or amount of polymer components (a), energy ray curable components (g), coupling agents (e), or crosslinking agents (f) contained in the film-type adhesive. These components will be explained in detail later.

[0033] <Example of film-type adhesive> Figure 1 is a schematic cross-sectional view showing an example of the film-like adhesive of this embodiment. Please note that the diagrams used in the following explanation may be enlarged for convenience in order to make the features of the present invention easier to understand, and the dimensional ratios of each component may not be the same as in reality.

[0034] The film-like adhesive 13 shown in Figure 1 has a first release film 151 on one side (sometimes referred to as the "first side" in this specification) 13a and a second release film 152 on the other side (sometimes referred to as the "second side" in this specification) 13b opposite to the first side 13a. Such a film-like adhesive 13 is suitable for storage, for example, in the form of a roll.

[0035] The film-like adhesive 13 is intended for cutting by plasma irradiation and has energy ray curing properties. The tack reduction rate of the film-like adhesive 13 is 0.12 or higher.

[0036] The first release film 151 and the second release film 152 may both be known types. The first release film 151 and the second release film 152 may be the same as each other, or they may be different from each other, for example, having different peeling forces required to peel them off the film-like adhesive 13.

[0037] Either the first surface 13a or the second surface 13b of the film-like adhesive 13 becomes the surface for attachment to one side of the wafer, and the other becomes the surface for attachment to the support sheet described later.

[0038] <Other components of film-type adhesives> The film-like adhesive may consist of one layer (single layer) or of two or more layers. If the film-like adhesive consists of multiple layers, these layers may be identical or different from each other, and there are no particular limitations on the combination of these layers.

[0039] 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."

[0040] The thickness of the film-like adhesive is preferably 1 to 70 μm, more preferably 2 to 50 μm, and particularly preferably 3 to 30 μm. When the thickness of the film-like adhesive is above the lower limit, the strength of the film-like adhesive is increased, and the effects obtained by using the film-like adhesive are also increased. When the thickness of the film-like adhesive is below the upper limit, it is avoided that the thickness of the film-like adhesive and its cured product becomes excessive. Here, "thickness of the film-like adhesive" refers to the total thickness of the film-like adhesive. For example, the thickness of a multi-layered film-like adhesive refers to the total thickness of all the layers that make up the film-like adhesive. This also applies to other layers such as the substrate, adhesive layer, and interlayer, which will be discussed later.

[0041] 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.

[0042] <<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.

[0043] In this specification, "room temperature" means a temperature that is neither cooled nor heated, i.e., a normal temperature, such as 18-28°C.

[0044] In a film-type adhesive, the ratio of the total content of one or more of the following components in the film-type adhesive to the total mass of the film-type adhesive shall not exceed 100% by mass. Similarly, in an adhesive composition, the ratio of the total content of one or more of the following components of the adhesive composition to the total mass of the adhesive composition shall not exceed 100% by mass.

[0045] 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.

[0046] Examples of the adhesive composition include a composition containing a polymer component (a) 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 a photopolymerization initiator (h). An adhesive composition for forming a film-like adhesive that has both energy ray curability and thermosetting properties preferably contains a polymer component (a), an energy ray curability component (g), and a thermosetting component (b), and more preferably contains a polymer component (a), an energy ray curability component (g), a photopolymerization initiator (h), a thermosetting component (b), and a curing accelerator (c).

[0047] The polymer component (a), energy ray curable component (g), photopolymerization initiator (h), thermosetting component (b), and curing accelerator (c) that may be 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.

[0048] <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.

[0049] Examples of polymer component (a) include acrylic resin, urethane resin, phenoxy resin, silicone resin, saturated polyester resin, etc., with acrylic resin being preferred.

[0050] 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 between 10,000 and 2,000,000, more preferably between 1,000,000 and 1,500,000, and may also be, for example, between 1,000,000 and 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. On the other hand, if the weight-average molecular weight of the acrylic resin is above the lower limit, 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 film-like adhesive can more easily conform to the uneven surface of the adherend.

[0051] In this specification, "weight-average molecular weight" refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC) unless otherwise specified.

[0052] 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 support sheet described later. When the Tg of the acrylic resin is below the upper limit, the adhesive strength between the film-like adhesive and the chip is improved.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] Examples of the (meth)acrylic acid esters constituting the acrylic resin include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, 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.

[0057] The monomers that make up the acrylic resin may be just one type or two or more types, and if there are two or more types, their combination and ratio can be arbitrarily selected.

[0058] 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).

[0059] In the film-like adhesive, the ratio of the polymer component (a) content to the total mass of the film-like adhesive is preferably 40% by mass or less, regardless of the type of polymer component (a), and may be, for example, 35% by mass or less, 30% by mass or less, or 25% by mass or less. As will be described later, by irradiating the plasma-irradiated film-like adhesive with energy rays such as ultraviolet light, it becomes easier to pick up the adhesive-cured chips from the support sheet. On the other hand, the aforementioned ratio is greater than 0% by mass, and is preferably 8% by mass or more in that the effect obtained by using polymer component (a) is further enhanced.

[0060] The above-mentioned statement 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 40% by mass or less, regardless of the type of polymer component (a), for example, it may be 35% by mass or less, 30% by mass or less, or 25% by mass or less, while the aforementioned ratio is preferably greater than 0% by mass and 8% 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.

[0061] <Energy ray curing component (g)> The energy-ray curable component (g) facilitates the attachment of the film-like adhesive to the wafer at room temperature (e.g., room temperature), and further facilitates the pickup of the adhesive-cured chip from the support sheet. The energy-ray curable component (g) is an energy-ray curable nonpolymer, or an energy-ray curable oligomer or polymer (polymer) that can be considered to have been synthesized from an energy-ray curable nonpolymer.

[0062] The aforementioned energy-ray curable nonpolymer cannot be considered a monomer polymer and is a component that possesses energy-ray curability. Examples of the energy-ray curable nonpolymer include compounds having at least one polymerizable double bond in the molecule, and acrylate compounds having a (meth)acryloyl group are preferred.

[0063] Examples of the aforementioned acrylate compounds include trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. Examples include (meth)acrylates containing a chain-like aliphatic skeleton; cyclic aliphatic skeleton-containing (meth)acrylates such as dicyclopentanyl di(meth)acrylate and tricyclodecane dimethylol diacrylate; polyalkylene glycol (meth)acrylates such as polyethylene glycol di(meth)acrylate; oligoester (meth)acrylates; urethane (meth)acrylate oligomers; epoxy-modified (meth)acrylates; polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; and itaconic acid oligomers.

[0064] The molecular weight or weight-average molecular weight of the energy ray-curable component (g) is preferably 100 to 30,000, and more preferably 300 to 10,000.

[0065] 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 4% by mass or more, more preferably 6% by mass or more, and may be, for example, 7% by mass or more. When the ratio is above the lower limit, the energy-ray curing of the film-like adhesive becomes easier. On the other hand, the aforementioned ratio is preferably 20% by mass or less, in that it suppresses the excessive use of the energy ray curable component (g).

[0066] <Photopolymerization initiator (h)> Composition (III) and the film-like adhesive contain a photopolymerization initiator (h), which allows the polymerization reaction of the energy ray-curable component (g) to proceed efficiently.

[0067] Examples of the photopolymerization initiator (h) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one; and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl Examples include acylphosphine oxide compounds such as diphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone; and quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone. Furthermore, examples of photopolymerization initiators (h) include photosensitizers such as amines.

[0068] 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 12 parts by mass, more preferably 0.5 to 9 parts by mass, and even more preferably 1 to 6 parts by mass, based on the content of 100 parts by mass of the energy ray curable component (g).

[0069] <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.

[0070] [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.

[0071] (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.

[0072] 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.

[0073] 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.

[0074] When composition (III) and the film-like adhesive contain a dicyclopentadiene type epoxy resin and a bisphenol F type epoxy resin, the content of the dicyclopentadiene type epoxy resin in composition (III) and the film-like adhesive is preferably 3 to 12 times the mass of the content of the bisphenol F type epoxy resin, and more preferably 5 to 10 times the mass.

[0075] When composition (III) and the film-like adhesive contain a dicyclopentadiene type epoxy resin and a bisphenol F type epoxy resin, the ratio of the total content of the dicyclopentadiene type epoxy resin and the bisphenol F type epoxy resin to the content of epoxy resin (b1) in composition (III) and the film-like adhesive is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% 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.

[0076] (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.

[0077] 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).

[0078] 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.

[0079] 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.

[0080] When using a thermosetting component (b), the content of the thermosetting agent (b2) in composition (III) and the film-like adhesive is preferably 0.5 to 10 parts by mass per 100 parts by mass of epoxy resin (b1), for example, it may be 0.5 to 5 parts by mass or 0.5 to 3 parts by mass. When the content of the thermosetting agent (b2) is above the lower limit, the thermosetting of the film-like adhesive proceeds more easily. When the content of the thermosetting agent (b2) is below the upper limit, the moisture absorption rate of the film-like adhesive is reduced, and the reliability of the package obtained using the film-like adhesive is further improved.

[0081] When using a thermosetting component (b), the content of the thermosetting component (b) in composition (III) and the film-like adhesive (for example, the total content of epoxy resin (b1) and thermosetting agent (b2)) is preferably 20 to 1000 parts by mass, more preferably 100 to 1000 parts by mass, per 100 parts by mass of polymer component (a). For example, it may be any of 100 to 800 parts by mass and 100 to 500 parts by mass, or any of 200 to 1000 parts by mass and 300 to 1000 parts by mass, or 200 to 800 parts by mass. Having the content of the thermosetting component (b) within this range makes it easier to adjust the adhesive strength between the film-like adhesive and the support sheet described later.

[0082] <Curing accelerator (c)> The curing accelerator (c) is an ingredient used to adjust 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 aforementioned imidazoles as guest compounds.

[0083] 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, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the content of the thermosetting component (b) (for example, the total content of epoxy resin (b1) and thermosetting agent (b2)). When the content of the curing accelerator (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.

[0084] ○Other ingredients The adhesive composition may contain, or may not contain, any other components that do not fall under any of the following categories: polymer component (a), energy ray curable component (g), photopolymerization initiator (h), thermosetting component (b), or curing accelerator (c). 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.

[0085] <Filling material (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.

[0086] 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 ).

[0087] 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.

[0088] In the film-like adhesive, the ratio of the filler (d) content to the total mass of the film-like adhesive is preferably less than 15% by mass, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. As will be described later, when the film-like adhesive is cut by irradiating it with plasma, having the ratio within this range makes it easier to cut. On the other hand, the aforementioned ratio is 0% by mass or more. In terms of the ease of cutting 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).

[0089] <Coupling agent (e)> The film-type adhesive exhibits improved adhesion and bonding to the substrate by containing a coupling agent (e). Furthermore, the inclusion of a coupling agent (e) in the film-type adhesive improves the water resistance of the cured product without compromising its heat resistance. The coupling agent (e) has a functional group that can react with inorganic or organic compounds.

[0090] 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.

[0091] Preferred silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane (also known as 3-glycidoxypropyltrimethoxysilane; the same applies to other compounds hereafter), 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-(2-aminoethylamino)propyltrimethoxy Examples include sisilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfan, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, oligomeric or polymeric organosiloxanes, etc.

[0092] When a coupling agent (e) is used, 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 effects of using the coupling agent (e), such as improved dispersibility of the filler (d) in the resin and improved adhesion of the film adhesive to the adherend, are more pronounced. When the content of the coupling agent (e) is below the upper limit, outgassing is further suppressed.

[0093] <Crosslinking agent (f)> If polymer component (a) has functional groups such as vinyl groups, (meth)acryloyl groups, amino groups, hydroxyl groups, carboxyl groups, and isocyanate groups that can bond with other compounds, such as the acrylic resin mentioned above, the crosslinking agent (f) crosslinks the functional groups in polymer component (a) with other compounds. In this case, the initial adhesive strength and cohesive strength of the film-like adhesive can be adjusted.

[0094] 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).

[0095] 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).

[0096] <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.

[0097] 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.

[0098] <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. In particular, using a film-type adhesive containing an antioxidant (sometimes referred to as "antioxidant (j1)" in this specification) improves the pickability of the adhesive-cured chip. This is presumed to be because when plasma is irradiated onto the film-type adhesive, radicals that are normally unwanted are captured, and the composition of the adhesive-cured product ultimately becomes desirable. In other words, a preferred general-purpose additive (j) contained in composition (III) and the film-like adhesive is an antioxidant (j1).

[0099] Examples of antioxidants (j1) include hindered amine-based light stabilizers. Examples of the hindered amine-based light stabilizers include p,p'-dioctyldiphenylamine, phenyl-α-naphthylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N,N'-diphenyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diallyl-p-phenylenediamine, and 4,4'-(α,α-dimethylbenzyl)diphenylamine. p,p-toluenesulfonylaminodiphenylamine, N-phenyl-N'-(3-methchlorolyloxy-2-hydroxypropyl)-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine, alkylated diphenylamine, dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly[[6-( 1,1,3,3-Tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, 1,2,3,Mixed esters of 4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5 Examples include mixed esterified products with [5]undecane, mixed esterified products of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, (2,2,6,6-tetramethylene-4-piperidyl)-2-propylene carboxylate, (1,2,2,6,6-pentamethyl-4-piperidyl)-2-propylene carboxylate, etc.

[0100] Among these, the hindered amine light stabilizer is preferably a mixed ester of 1,2,3,4-butanetetracarboxylic acid, which is an N-alkyl type hindered amine light stabilizer, and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0101] 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.

[0102] When composition (III) and the film-like adhesive contain antioxidant (j1), the ratio of antioxidant (j1) content to the total mass of the film-like adhesive is preferably 0.05 to 15% by mass, for example, 0.1 to 10% by mass and 0.5 to 5% by mass. When the ratio is above the lower limit, the pickability of the adhesive-cured chip is improved. When the ratio is below the upper limit, excessive use of antioxidant (j1) is suppressed.

[0103] If composition (III) and the film adhesive contain a general-purpose additive (i) other than the antioxidant (j1), the ratio of the content of the general-purpose additive (i) other than the antioxidant (j1) to the total mass of the film adhesive may be, for example, 0.1 to 10% by mass.

[0104] <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.

[0105] 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.

[0106] 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.

[0107] <<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.

[0108] ◇Film-type adhesive composite sheet A film-like adhesive composite sheet according to one embodiment of the present invention comprises a support sheet and a film-like adhesive provided on one surface of the support sheet, wherein the film-like adhesive is the film-like adhesive according to the above-described embodiment of the present invention. The film-like adhesive composite sheet of this embodiment can be used, for example, as a sheet for cutting a film-like adhesive that has been attached to a wafer by irradiation with plasma. In either case, ultimately, as will be described later, the chip with the cured adhesive obtained after plasma irradiation is pulled away from the support sheet and picked up. In the film-like adhesive composite sheet of this embodiment, the tack reduction rate of the film-like adhesive is 0.12 or higher, so that the adhesive-cured chip can be easily peeled off the support sheet and picked up normally from the support sheet, resulting in high pickability.

[0109] 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.

[0110] <<Support Sheet>> Examples of the support sheet include one consisting only of a base material; one comprising a base material and an adhesive layer provided on one surface of the base material; and one constructed by laminating a base material, an adhesive layer, and an intermediate release layer in this order in the thickness direction.

[0111] If the support sheet comprises the base material and the adhesive layer, in the film-like adhesive composite sheet, the adhesive layer is positioned between the base material and the film-like adhesive. When the support sheet comprises the base material, adhesive layer, and intermediate release layer, in the film-like adhesive composite sheet, the adhesive layer and the intermediate release layer are arranged between the base material and the film-like adhesive in this order, from the base material side toward the film-like adhesive side. The adhesive layer and the intermediate release layer are layers designed to facilitate the pickup of the adhesive-cured chips, described later, from the support sheet.

[0112] Since the film-like adhesive has energy ray curing properties, it is preferable that the support sheet consists only of the base material, as this simplifies the structure of the support sheet.

[0113] The base material, adhesive layer, and intermediate release layer may each consist of one layer (single layer) or two or more layers. If they consist of multiple layers, these layers may be identical or different, and the combination of these layers is not particularly limited.

[0114] Figure 2 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 2 comprises a support sheet 10 and a film-like adhesive 13 provided on one surface (sometimes referred to as the "first surface" in this specification) 10a of the support sheet 10. The film-like adhesive 13 is the film-like adhesive 13 shown in Figure 1.

[0115] The support sheet 10 consists only of the base material 11, and one side (first side) 10a of the support sheet 10 is the same as one side 11a of the base material 11. The other side (the side opposite to the film-like adhesive 13) 10b of the support sheet 10 is the same as the other side 11b of the base material 11.

[0116] In the film-like adhesive composite sheet 101, a jig adhesive layer 16 is provided in the region near the peripheral edge of the film-like adhesive 13 (a region with an annular planar shape along the peripheral edge) of the first surface 13a of the film-like adhesive 13 that is opposite to the support sheet 10 side.

[0117] The film-like adhesive composite sheet 101 further includes a release film 15 in the area of ​​the first surface 13a of the film-like adhesive 13 where the jig adhesive layer 16 is not provided. The release film 15 is further provided on the jig adhesive layer 16 in the area near the peripheral edge of the film-like adhesive 13. In the film-like adhesive composite sheet 101, the release film 15 has any configuration.

[0118] The film-like adhesive composite sheet 101 is used by attaching a wafer to the first surface 13a of the film-like adhesive 13 after the release film 15 has been removed. The side of the jig adhesive layer 16 opposite to the film-like adhesive 13 is attached to the fixing jig.

[0119] 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.

[0120] For example, the support sheet 10 may be constructed by laminating a base material 11 and an adhesive layer in that order in the thickness direction toward the film-like adhesive 13 side, or by laminating a base material 11, an adhesive layer, and an intermediate release layer in that order in the thickness direction.

[0121] In this embodiment, the film-like adhesive composite sheet includes an adhesive layer, and if a portion of the surface of the adhesive layer opposite to the substrate side is exposed, it does not need to include a jig adhesive layer.

[0122] Next, each layer constituting the film-like adhesive composite sheet of this embodiment will be described in more detail.

[0123] <Base material> The substrate may be in the form of a sheet or a film, and may be one of known types. The substrate is preferably one that allows energy rays to pass through. 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.

[0124] 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.

[0125] In addition to the main constituent materials such as the aforementioned resin, the base material may also contain various known additives such as fillers, colorants, antioxidants, organic lubricants, catalysts, and plasticizers.

[0126] The substrate thickness is preferably 50 to 300 μm. A substrate thickness within this range improves the flexibility of the film-like adhesive composite sheet and its suitability for adhesion to wafers.

[0127] The surface of the substrate may or may not be treated with oxidation, lipophilicity, hydrophilicity, or primer treatment, and may or may not have other layers deposited on it.

[0128] 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.

[0129] <Adhesive layer> The adhesive layer is in the form of a sheet or film and contains an adhesive. Examples of the adhesive include adhesive resins such as acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester resin. The adhesive layer is preferably one that allows energy rays to pass through.

[0130] The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 100 μm.

[0131] The adhesive layer may be either energy-ray curable or non-energy-ray curable. If the adhesive layer is energy-ray curable, the chip with the cured adhesive can be picked up more easily by curing the adhesive layer with energy rays before picking it up from the support sheet. In this embodiment, the support sheet after the adhesive layer has been cured by energy rays is also simply referred to as a support sheet, as long as the other laminated structures are maintained.

[0132] The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition can be applied to the surface on which the adhesive layer is to be formed, and then dried as necessary to form the adhesive layer in the desired location. The coating and drying of the adhesive composition can be carried out, for example, in the same manner as in the coating and drying of the adhesive composition described above.

[0133] <Intermediate delamination layer> The aforementioned intermediate release layer may be in the form of a sheet or a film, and may be of a known type. Examples of intermediate release layers include an intermediate release layer consisting of a single resin layer, and an intermediate release layer consisting of multiple layers comprising a resin body (resin layer) and a release treatment layer provided on one side of the body. In the intermediate release layer with the release treatment layer, the release treatment layer is positioned in the film-like adhesive composite sheet facing the film-like adhesive side. The intermediate delamination layer is preferably made of a material that allows energy rays to pass through.

[0134] Both the resin layer in the intermediate release layer equipped with a release treatment layer and the intermediate release layer consisting of a single resin layer can be manufactured by molding a resin composition containing resin. An intermediate release layer equipped with a release treatment layer can be produced by performing a release treatment on one side of the resin layer.

[0135] The aforementioned stripping treatment can be carried out using various known stripping agents, such as alkyd, silicone, fluorine, unsaturated polyester, polyolefin, or wax-based agents.

[0136] Examples of resins that make up the resin layer in an intermediate release layer equipped with a release treatment layer include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene (PE), and polypropylene (PP). Examples of the resin that constitutes the intermediate release layer, which consists of a single layer of resin, include ethylene-vinyl acetate copolymer and the like.

[0137] The thickness of the intermediate delamination layer is preferably 10 to 200 μm. When the thickness of the intermediate delamination layer is greater than or equal to the lower limit, the handling of the intermediate delamination layer is improved, and the effect of suppressing damage such as cutting of the intermediate delamination layer is further enhanced. When the thickness of the intermediate delamination layer is less than or equal to the upper limit, when the adhesive-cured chip is picked up, the upward force from the support sheet side is more easily transmitted to the adhesive-cured chip, making the pickup easier.

[0138] <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).

[0139] <Adhesive layer for jigs> The adhesive layer for the jig may be of known origin. The adhesive layer for the jig may be, for example, a single-layer structure containing adhesive components, or a multi-layer structure in which layers containing adhesive components are laminated on both sides of a core sheet.

[0140] <Other layers> The film-like adhesive composite sheet of this embodiment may or may not have any other layers at any location that do not fall under any of the following categories: the base material, the adhesive layer, the intermediate release layer, the film-like adhesive, the release film, or the jig adhesive layer. The aforementioned other layers can be arbitrarily selected depending on the purpose and are not particularly limited.

[0141] In this embodiment, it is preferable that the film-like adhesive composite sheet does not have any other layers between the support sheet and the film-like adhesive. Using such a film-like adhesive composite sheet improves the pickability of the adhesive-cured chip.

[0142] <<The peeling force between the energy-ray cured film-like adhesive and the support sheet>> The degree of pickability of the adhesive-cured chip when using the film-like adhesive composite sheet of this embodiment can be determined by using the peeling force between the energy-ray cured film-like adhesive (adhesive cured product) and the support sheet as an indicator.

[0143] In this embodiment, the film-like adhesive composite sheet is subjected to an illuminance of 230 mW / cm² from the support sheet side. 2 , light intensity 190mJ / cm 2A test piece (T3) with a width of 25 mm is prepared by irradiating the film-like adhesive with energy rays under the specified conditions to cure it with energy rays. In the test piece (T3), the support sheet is peeled off from the energy-ray cured film-like adhesive, and the angle between the surface of the energy-ray cured film to which the support sheet was attached and the surface of the support sheet to which the energy-ray cured film was attached is set to 180°. When a peel test (so-called 180° peel) is performed in which the support sheet is peeled off from the energy-ray cured film-like adhesive in its longitudinal direction at a peeling speed of 300 mm / min, it is preferable that the peeling force between the energy-ray cured film-like adhesive and the support sheet is 100 mN / 25 mm or less. By using such a film-like adhesive composite sheet, the pickability of the adhesive-cured chip is further improved.

[0144] The aforementioned peel test can be carried out in more detail, for example, by the following method. Specifically, first, a rectangular section with a width of 25 mm and a length of preferably 200 mm or more is cut from the film-like adhesive composite sheet. Then, an illuminance of 230 mW / cm is applied to this section from the support sheet side. 2 , light intensity 190mJ / cm 2 By irradiating the section with energy rays (e.g., ultraviolet light) under these conditions, the film-like adhesive in the section is cured by energy rays, and a test specimen (T3) is prepared. As the film-like adhesive composite sheet, one with a release film as shown in Figure 2 may be used, and the test specimen (T3) may or may not have a release film.

[0145] Next, the support sheet is peeled off the energy-ray cured film-like adhesive in the test specimen (T3). At this time, it is preferable to fix the test specimen (T3) to the rigid support by attaching the cured material to the rigid support using adhesive means such as double-sided tape, and then measure the peel force using this fixed test specimen (T3). Fixing the test specimen (T3) in this way allows for more accurate measurement of the peel force. As the rigid support, a material that does not deform during the measurement of the peel force can be used, and a plate-shaped or block-shaped material made of resin or metal is preferred. The fixation of the test specimen (T3) to the rigid support is preferably carried out under conditions of 23°C and 50% relative humidity (RH). When fixing the test specimen (T3) to the rigid support, it is preferable to press the laminate, which consists of the rigid support, the adhesive means, and the test specimen (T3), by pressing a rubber roller against the laminate and moving it back and forth. Before measuring the peel force, it is preferable to allow the test specimen (T3), after being fixed to the rigid support, to stand for at least 30 minutes in an environment with a temperature of 23°C and a relative humidity (RH) of 50% to stabilize its fixed state. By performing one or all of these steps and securely fixing the test specimen (T3) to the rigid support, the peeling force can be measured with greater accuracy.

[0146] In the test specimen (T3), the peeling of the support sheet from the energy-ray cured film-like adhesive is performed with the cured material fixed so that the surfaces that were in contact with each other form a 180° angle. The peeling speed shall be 300 mm / min. The measured peel force obtained at this time is adopted as the peel force between the energy-ray cured film-like adhesive and the support sheet.

[0147] The peel force between the energy-ray cured film-like adhesive and the support sheet is more preferably 70 mN / 25 mm or less, and even more preferably 40 mN / 25 mm or less. On the other hand, in terms of being highly effective in suppressing the peeling of the adhesive-cured chip from the support sheet for purposes other than intended, it is preferable that the peeling force be 10 mN / 25 mm or more.

[0148] The peeling force between the energy-ray cured film-like adhesive and the support sheet can be adjusted, for example, by adjusting the type or amount of components contained in the film-like adhesive. In particular, the peeling force can be adjusted more easily by adjusting the type or amount of polymer components (a), energy-ray curable components (g), coupling agents (e), or crosslinking agents (f) contained in the film-like adhesive.

[0149] ◇Method of manufacturing a film-like adhesive composite sheet The film-like adhesive composite sheet of this embodiment can be manufactured by laminating the above-mentioned layers in corresponding positional relationships and, if necessary, adjusting the shape of some or all of the layers. The method for forming each layer is as described above. 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.

[0150] For example, when laminating a film-like adhesive onto a support sheet, the adhesive composition is applied to a release film and dried as needed to form a film-like adhesive on the release film. Then, the exposed surface of this film-like adhesive is bonded to one side of the support sheet. When manufacturing a support sheet having a laminated structure of a substrate and an adhesive layer, for example, an adhesive composition can be applied to a release film and dried as necessary to form an adhesive layer on the release film, and the exposed surface of this adhesive layer can be bonded to one surface of the substrate. When laminating an intermediate release layer onto a substrate, the intermediate release layer should be prepared in advance using the same method as for the adhesive layer, and then laminated onto the desired lamination location (for example, the adhesive layer).

[0151] ◇Manufacturing method for chips with cured adhesive (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. By using the aforementioned film-like adhesive composite sheet, during the manufacturing of adhesive-cured chips, the film-like adhesive can be cut by plasma irradiation, and then cured by energy rays, allowing the adhesive-cured chips to be picked up normally from the support sheet.

[0152] A method for manufacturing an adhesive-cured chip according to one embodiment of the present invention is a method for manufacturing an adhesive-cured chip using a film-like adhesive composite sheet according to the above-described embodiment of the present invention, In the above manufacturing method, the film-like adhesive in the film-like adhesive composite sheet is attached to one side of a wafer, and the wafer and the film-like adhesive are irradiated with plasma to divide the wafer and produce chips, and the film-like adhesive is cut, and the cut film-like adhesive is cured with energy rays to produce chips with cured adhesive, and the chips with cured adhesive are pulled away from the support sheet and picked up.

[0153] The manufacturing method described above may be the same as the conventional method for manufacturing chips with cured adhesive, except that the film-like adhesive composite sheet of this embodiment described above is used instead of the conventional film-like adhesive composite sheet.

[0154] In the above manufacturing method, the attachment of the film-like adhesive composite sheet to the wafer can be carried out by a known method, and it is preferable to do so at room temperature (e.g., room temperature).

[0155] In the above manufacturing method, preferred gases used to generate plasma during plasma irradiation include, for example, oxygen (O2) gas, sulfur hexafluoride (SF6) gas, and methane tetrafluoride (CF4) gas. The flow rate of the gas used to generate the plasma is preferably 50 to 300 cc. The output power during plasma irradiation is preferably 200 to 400 watts.

[0156] In the manufacturing method described above, the irradiation conditions (illuminance, light intensity) for curing the film-like adhesive with energy rays are as explained earlier.

[0157] In the above manufacturing method, the adhesive-cured chip can be picked up by a known method. During pickup, if the support sheet consists only of a substrate, the adhesive-cured chip will peel off from the substrate. If the support sheet has an adhesive layer as its outermost layer, the adhesive-cured chip will peel off, for example, from the adhesive layer or its energy-ray cured product. If the support sheet has an intermediate release layer as its outermost layer, the adhesive-cured chip will peel off from the intermediate release layer. Regardless of the type of support sheet, the pickability of the adhesive-cured chip is high.

[0158] <<Modified Method of Manufacturing Chips with Cured Adhesive>> In the method for manufacturing a chip with an adhesive cured product according to this embodiment, other steps not corresponding to the above-described steps (attaching a film-like adhesive composite sheet to a wafer, irradiating the wafer and the film-like adhesive with plasma, irradiating the film-like adhesive after cutting with energy rays, and picking up the chip with the adhesive cured product) may be performed or omitted, as long as they do not impair the effects of the present invention. The types and timings of the aforementioned other processes can be arbitrarily selected according to the purpose, and can also be arbitrarily selected according to the type of film-like adhesive composite sheet or wafer, and are not particularly limited.

[0159] In the manufacturing method of this embodiment, the wafer is divided and the film-like adhesive is cut in succession by plasma irradiation on the support sheet. However, the wafer may be divided in advance, and only the film-like adhesive may be cut by plasma irradiation. In that case, instead of the wafer with the film-like adhesive composite sheet, a chip group holder is used, in which a plurality of chips are aligned and held on the side of the film-like adhesive in the film-like adhesive composite sheet that is opposite to the side of the support sheet. The wafer is not divided, only the film-like adhesive is cut, and the rest is the same as the manufacturing method described above, thereby producing a chip with an adhesive cured product. The chip group holder can be manufactured by known methods.

[0160] ◇Manufacturing method for substrate devices (Method of using chips with adhesive curing material) A substrate device can be manufactured using the adhesive-cured chip obtained by the manufacturing method described above. The substrate device can be manufactured by known methods, except for the use of the aforementioned adhesive-cured chip. For example, the adhesive-cured chip is bonded to a circuit board by the adhesive curing material (energy-ray cured film-like adhesive) within it and mounted. If the film-like adhesive is thermosetting, the energy-ray cured film-like adhesive is further thermocured after mounting. Furthermore, by adding other processes as necessary, the desired substrate device can be manufactured. [Examples]

[0161] 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. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or other reasons, measurements can be taken using other instruments with equivalent performance.

[0162] <<Raw materials for resin manufacturing>> In this example and comparative example, "MA" is abbreviated as methyl acrylate, and "HEA" is abbreviated as 2-hydroxyethyl acrylate.

[0163] <<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 obtained by copolymerizing MA (85 parts by mass) and HEA (15 parts by mass) (weight-average molecular weight 400,000, glass transition temperature 6°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) [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) [Curing accelerator (c)] (c)-1:2-phenyl-4,5-dihydroxymethylimidazole (Shikoku Chemicals Co., Ltd. "Curesol (registered trademark) 2PHZ-PW") [Coupling agent (e)] (e)-1:3-Glycidoxypropyltrimethoxysilane-added silicate compound ("MKC® Silicate MSEP-2" manufactured by Mitsubishi Chemical Corporation) [Antioxidant (j1)] (j1)-1: Mixed esterified product of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (hindered amine light stabilizer, ADEKA Corporation's "ADEKA Stab (registered trademark) LA-63P")

[0164] [Example 1] <<Manufacturing of film-type adhesives>> <Manufacturing of adhesive compositions> A thermosetting adhesive composition was prepared by dissolving or dispersing each component in methyl ethyl ketone so that the types and amounts of components contained in the film adhesive are as shown in Table 1, and stirring at 23°C, resulting in a total concentration of 50% by mass of all components other than the solvent.

[0165] <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 silicone for release, was used. The adhesive composition obtained above was applied to the treated surface and dried at 100°C for 1 minute to produce a 5 μm thick film-like adhesive that possesses both energy ray curability and thermosetting properties. Hereinafter, these film-like adhesives may be referred to as "film-like adhesive (F1)" in this specification. 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 (film-like adhesive (F1)) that does not have a second release film, a film-like adhesive with a release film was manufactured, comprising a film-like adhesive, a first release film provided on one side of the film-like adhesive, and a second release film provided on the other side of the film-like adhesive.

[0166] <<Evaluation of film-type adhesives>> <Measurement of probe tack value T0 of film-like adhesive before plasma irradiation> The probe tack value T0 was measured using the following procedure. The film-like adhesive with release film obtained above was cut into small pieces measuring 10 mm x 10 mm. Next, the second release film was removed from the obtained pieces to obtain test samples. Then, under conditions of 23°C and 50% RH (relative humidity), the probe tack value on the surface of the film-like adhesive of the test samples, exposed after removing the second release film, was measured using a tacking tester (manufactured by Nippon Tokushu Sokki Co., Ltd., product name "NTS-4800"). Specifically, a 5mm diameter stainless steel probe was subjected to a contact load of 1000gf / cm² at a speed of 0.1cm / s for 1 second. 2 (That is, 9.81 N / cm²) 2 After peeling off the second release film and bringing the probe into contact with the surface of the film-like adhesive of the test sample, the force required to lift the probe from the surface of the test sample at a speed of 0.1 cm / s was measured, and the obtained value was defined as the probe tack value T0 of the test sample. The measured values ​​for T0 are shown in the "Probe Tack Value T0" column of Table 1.

[0167] <Measurement of probe tack value Tb after plasma irradiation and before UV irradiation> The probe tack value Tb was measured using the following procedure. The film-like adhesive with release film obtained above was cut into small pieces measuring 10 mm x 10 mm. Next, the second release film was removed from the obtained pieces to obtain the test sample. Then, using a plasma dry cleaner "PDC210" manufactured by Yamato Chemical Co., Ltd., the test sample was placed inside the device, and the device was evacuated for 15 minutes to create a vacuum inside the device. Next, the test sample was irradiated with plasma for 1 minute under the conditions of gas type O2, flow rate 100 mL / min, and output 300 W. Next, the test sample was removed from the device and allowed to cool in an air atmosphere, and the atmosphere inside the device was replaced with air. Next, the device was evacuated again under the same conditions as above, the test sample was irradiated with plasma inside the device, the test sample was removed from the device and allowed to cool in an air atmosphere, and the atmosphere inside the device was replaced with air. Furthermore, under the same conditions as described above, the test sample was subjected to plasma irradiation for a total of 15 minutes by repeating the process of vacuuming the device, irradiating it with plasma, and cooling it 13 times (a total of 15 times).

[0168] Next, in the same manner as the measurement of the probe tack value T0, the probe tack value Tb was measured on the surface of the film-like adhesive of the test sample, which was exposed after peeling off the second release film. The measured values ​​for Tb are shown in the "Probe Tack Value Tb" column of Table 1.

[0169] <Measurement of probe tack value Ta after plasma irradiation and UV irradiation> The probe tack value Ta was measured using the following procedure. The film-like adhesive with release film obtained above was cut into small pieces measuring 10 mm x 10 mm. Next, the second release film was removed from the obtained pieces to obtain test samples. Then, the test samples were irradiated with plasma in the same manner as described above for measuring the probe tack value Tb. Next, the plasma-irradiated test sample was subjected to ultraviolet irradiation using a high-pressure mercury lamp-equipped ultraviolet irradiation device (Lintec Corporation's "RAD2010") in an air atmosphere at an illuminance of 230 mW / cm². 2 , light intensity 190mJ / cm2 Under these conditions, the film-like adhesive was cured by irradiating it with ultraviolet light.

[0170] Next, in the same manner as the measurement of the probe tack value T0, the probe tack value Ta was measured on the surface of the film-like adhesive of this test sample, which was exposed by peeling off the second release film. The measured values ​​of Ta are shown in the "Probe Tack Value Ta" column of Table 1.

[0171] <Calculation of Tack Reduction Rate> From the above probe tack values ​​Ta and Tb, the tack reduction rate X was calculated as (Tb-Ta) / Tb. The tack reduction rate X is shown in the "Tack Reduction Rate" column of Table 1.

[0172] <<Manufacturing of film-like adhesive composite sheets>> The first release film was removed from the film-like adhesive with release film obtained above (film-like adhesive thickness: 5 μm). A film-like adhesive composite sheet was manufactured by using a support sheet (a support sheet consisting only of a base material) (s1) (thickness 80 μm) and laminating the exposed side of a film-like adhesive, opposite to the side with the second release film, to one side of the support sheet. This film-like adhesive composite sheet is a film-like adhesive composite sheet with a release film, constructed by laminating a support sheet consisting only of a base material, a film-like adhesive, and a second release film in this order in the thickness direction. The support sheet (s1) has a three-layer structure in which a linear low-density polyethylene layer, a polypropylene layer, and a linear low-density polyethylene layer are laminated.

[0173] <<Manufacturing of silicone chips with cured adhesive>> Silicone chips with cured adhesive were manufactured using the following procedure.

[0174] <Fabrication of silicon chip cluster holders> Using a half-cut dicer (DISCO "DFG6363"), half-cuts were performed on the 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 the silicon wafer, a backgrind tape (Lintec's "Adwill E-3125KN") was applied to the grooved surface, and the back surface of the silicon wafer was ground using a polishing device (DISCO's "DFG8761") to reduce the thickness of the non-grooved portion of the silicon wafer to 50 μm. By creating grooves on the ground surface of the silicon wafer, the silicon wafer was divided at the grooved portion, and silicon chips (0.5 mm x 0.5 mm) were fabricated.

[0175] In the film-like adhesive composite sheet obtained above, the second release film was removed, and the exposed surface of the film-like adhesive was collectively attached to the back surface (grinding surface) of the group of silicon chips (silicon chip group) obtained above at room temperature. Next, the backgrind tape was irradiated with ultraviolet light to cure the adhesive layer in the backgrind tape, and the backgrind tape was removed from the silicon chip group. Based on the above, a silicon chip holder was fabricated in which multiple silicon chips are aligned and held on the side of the film adhesive in the film adhesive composite sheet that is opposite to the side of the support sheet.

[0176] Prior to evaluation, the silicon wafer was pre-divided because it had been confirmed that even when the silicon wafer was divided into a group of silicon chips and evaluated using these silicon chips and a film-like adhesive composite sheet, the same evaluation results could be obtained as when the undivided silicon wafer and film-like adhesive composite sheet were used. Furthermore, using silicon chips and a film-like adhesive composite sheet allows for simpler and more accurate evaluation. This also applies to the other examples and comparative examples described later.

[0177] <Fabrication of silicon chips with film-like adhesive> Using the silicon chip group holder obtained above, the film-like adhesive exposed between the silicon chips was cut along the silicon chips by irradiating it with plasma. More specifically, a plasma dry cleaner "PDC210" manufactured by Yamato Chemical Co., Ltd. was used as the apparatus. After placing the silicon chip group holder inside this apparatus, the apparatus was evacuated for 15 minutes to create a vacuum. Next, the film-like adhesive was irradiated with plasma for 1 minute under the conditions of gas type O2, flow rate 100 mL / min, and output 300 W. Then, the silicon chip group holder was removed from the apparatus and allowed to cool in an air atmosphere, and the atmosphere inside the apparatus was replaced with air. Next, the apparatus was evacuated again under the same conditions as above, the film-like adhesive in the silicon chip group holder was irradiated with plasma inside the apparatus, the silicon chip group holder was removed from the apparatus and allowed to cool in an air atmosphere, and the atmosphere inside the apparatus was replaced with air. Furthermore, under the same conditions as above, the vacuuming of the apparatus, the irradiation of the film-like adhesive with plasma, and the cooling of the silicon chip group holder were repeated 13 times (a total of 15 times), thereby irradiating the film-like adhesive with plasma for a total of 15 minutes, which cut the film-like adhesive exposed between the silicon chips. The reason for irradiating the film-like adhesive with plasma while cooling the silicon chip group holder was to prevent excessive temperature rise of the film-like adhesive due to plasma irradiation. Based on the above, a film-like adhesive-coated silicon chip was manufactured, comprising a silicon chip and a pre-cut film-like adhesive provided on the back surface of the silicon chip. These multiple film-like adhesive-coated silicon chips were aligned and held on a support sheet (s1), and together with the support sheet (s1), they constituted a group of film-like adhesive-coated silicon chips.

[0178] <Fabrication of silicone chip groups with cured adhesive> The film adhesive in the group of silicon chips with film adhesive obtained above was subjected to ultraviolet irradiation using a high-pressure mercury lamp equipped with an ultraviolet irradiation device (Lintec Corporation "RAD2010m / 12") under a nitrogen gas atmosphere at an irradiance of 220 mW / cm². 2 , light intensity 190mJ / cm 2 Under these conditions, the film-like adhesive was cured by irradiating it with ultraviolet light. As a result, multiple silicone chips with cured adhesive, each comprising a silicone chip and an ultraviolet-cured film-like adhesive provided on the back surface of the silicone chip, were fabricated on a support sheet (s1). These multiple silicone chips with cured adhesive were aligned and held on the support sheet (s1), and together with the support sheet (s1), they constituted a group of silicone chips with cured adhesive. The shape of the group of silicone chips with cured adhesive, when viewed from above, was approximately circular.

[0179] (Manufacturing of silicone chips with cured adhesive) Using a pickup die bonding device (Canon Machinery Co., Ltd. "BESTEM D-510"), we attempted to obtain the desired adhesive-cured silicon chip by picking it up from a group of adhesive-cured silicon chips by pulling it away from the support sheet (s1). In this case, the group of adhesive-cured silicon chips was viewed from above, and a central part and two line segments extending perpendicularly from the central part to just before the periphery of the group of adhesive-cured silicon chips were defined. Two locations were selected from the central part or its vicinity, and two locations each (a total of eight locations) were selected from both ends of the line segments or their vicinity, thereby selecting a total of 10 locations in the group of adhesive-cured silicon chips. One adhesive-cured silicon chip was picked up from each location, for a total of 10 adhesive-cured silicon chips. The pin pushing speed was set to 5 mm / s and the pin pushing height to 200 μm, and one adhesive-cured silicon chip was pushed up from the support sheet (s1) side by five pins.

[0180] <<Evaluation of film-type adhesive composite sheets>> <Evaluation of the pickability of silicone chips with cured adhesive> Following the pickup described above, the pickup properties of the adhesive-cured silicone chips were evaluated according to the following criteria. The results are shown in the "Pickup Properties" column of Table 1. [Evaluation Criteria] A: We were able to successfully pick up 10 silicone chips with cured adhesive. B: We were able to successfully pick up 9 silicone chips with cured adhesive. C: Successfully picked up 6-8 silicone chips with cured adhesive. D: Failed to successfully pick up 5 or more silicone chips with cured adhesive.

[0181] <Measurement of peeling force between energy-ray cured film-like adhesive and support sheet> From the film-like adhesive composite sheet with release film obtained above, rectangular sections measuring 25 mm x 250 mm were cut out. Next, an illuminance of 220 mW / cm² is applied to this section from the support sheet side. 2 , light intensity 190mJ / cm 2 By irradiating the section with ultraviolet light under these conditions, the film-like adhesive in the section was cured with ultraviolet light, and a test specimen (T3) with a release film was prepared.

[0182] Next, double-sided tape was attached to one side of a rigid support made of polystyrene board, while the release film was removed from the test piece (T3). Then, the exposed surface of the UV-cured film-like adhesive in the test piece (T3) was attached to the exposed surface of the double-sided tape (the side opposite to the side attached to the rigid support). At this time, the entire exposed surface of the UV-cured film-like adhesive was attached to the exposed surface of the double-sided tape. Under conditions of 23°C and 50% relative humidity (RH), the rigid support, double-sided tape, and test specimen (T3) were laminated together. A 2kg rubber roller was passed back and forth once on the rigid support to press down on the laminate, thereby fixing the test specimen (T3) to one side of the rigid support via the double-sided tape.

[0183] Next, this test specimen (T3) was fixed to a rigid support and left to stand for 30 minutes in an environment of 23°C and 50% relative humidity (RH). Next, using a universal tensile testing machine (Shimadzu Corporation's "Autograph AG-IS"), the support sheet (s1) was peeled off the UV-cured film adhesive in the test specimen (T3). The angle between the side of the UV-cured film adhesive to which the support sheet (s1) was attached and the side of the support sheet (s1) to which the UV-cured film adhesive was attached was set to 180°. A peel test (180° peel) was then performed, in which the support sheet (s1) was peeled off from the UV-cured film adhesive in its longitudinal direction at a peel speed of 300 mm / min. The peel force at this time was adopted as the peel force between the UV-cured film adhesive and the support sheet. The results are shown in the "Peel Force (mN / 25mm)" column in Table 1.

[0184] <<Manufacturing and evaluation of film-type adhesives, manufacturing of silicone chips with cured adhesives, and manufacturing and evaluation of film-type adhesive composite sheets>> [Example 2, Comparative Examples 1-2] A film-like adhesive was manufactured using the same method as in Example 1, except that the proportions of the components in the adhesive composition were changed. The types and contents of the components contained in these film-like adhesives are shown in Table 1. In addition, a "-" in the column for the components of the film-type adhesive means that the film-type adhesive does not contain that component.

[0185] Furthermore, a composite sheet with a film-like adhesive was manufactured using the same method as in Example 1, except that these film-like adhesives were used. These film-like adhesives and film-like adhesive composite sheets were evaluated using the same method as in Example 1. The results are shown in Table 1. Hereinafter, in this specification, the film-like adhesive obtained in Example 2 may be referred to as "film-like adhesive (F2)". Also, the film-like adhesives obtained in Comparative Examples 1 and 2 may be referred to as "film-like adhesive (FR1)" and "film-like adhesive (FR2)", respectively.

[0186] <<Manufacturing of silicone chips with cured adhesive>> <Fabrication of silicon chip cluster holders> A silicon chip group holder was fabricated using the same method as in Example 1.

[0187] <Fabrication of silicon chips with film-like adhesive> The film-like adhesive (film-like adhesive (F1)) in the silicon chip group holder obtained above was cured by irradiating it with ultraviolet light under the same conditions as in Example 1. As a result, a cured silicon chip group holder was produced in which multiple silicon chips were aligned and held on the UV-cured film-like adhesive.

[0188] <Fabrication of silicone chip groups with cured adhesive> Using the cured silicon chip group holder obtained above, plasma was irradiated onto the UV-cured film-like adhesive exposed between the silicon chips within the holder under the same conditions as in Example 1, thereby cutting the UV-cured film-like adhesive along the silicon chips. This produced a silicon chip with adhesive curing, comprising a silicon chip and the cut UV-cured film-like adhesive provided on the back surface of the silicon chip. These multiple silicon chips with adhesive curing were aligned and held on a support sheet (s1), and together with the support sheet (s1), they constituted a group of silicon chips with adhesive curing. The shape of the group of silicon chips with adhesive curing, when viewed from above, was approximately circular.

[0189] <Manufacturing of silicone chips with cured adhesive> Using the group of adhesive-cured silicon chips obtained above, we attempted to obtain the desired adhesive-cured silicon chip by picking up the adhesive-cured silicon chips from the group of adhesive-cured silicon chips from the support sheet (s1) in the same manner as in Example 1.

[0190] <<Evaluation of film-type adhesive composite sheets>> <Evaluation of the pickability of silicone chips with cured adhesive> After picking up the silicone chips coated with the cured adhesive as described above, the pickability of the silicone chips coated with the cured adhesive was evaluated using the same method as in Example 1. The results are shown in Table 1.

[0191] [Table 1]

[0192] As is clear from the results above, in Examples 1 and 2, the film-like adhesive was cut by plasma irradiation, and then cured by energy rays. The resulting silicon chip with the cured adhesive could then be successfully picked up from the support sheet. In Examples 1 and 2, it was hypothesized that the curing reaction of the film-like adhesive progressed due to ultraviolet irradiation, eliminating anchoring caused by plasma irradiation, and as a result, the pickability of the adhesive-cured chip was improved. In Examples 1 and 2, the peel force between the UV-cured film-like adhesive and the support sheet was 30 mN / 25 mm, which was small within an appropriate range. This result was consistent with the high pickability observed in these examples, as described above. In Examples 1 and 2, the tack reduction rate was 0.12 or higher.

[0193] In contrast, in Comparative Examples 1 and 2, the pickability of the silicon chips with the cured adhesive obtained after cutting the film-like adhesive by plasma irradiation and then curing it with energy rays was significantly inferior. In Comparative Examples 1 and 2, the curing reaction of the film-like adhesive by UV irradiation was slow, making it difficult to eliminate anchoring by plasma irradiation, and thus it was presumed that the pickability of the chip with the cured adhesive was poor. [Industrial applicability]

[0194] This invention can be used in the manufacture of substrate devices. [Explanation of Symbols]

[0195] 10...Support sheet, 10a...First side of support sheet 101...Film-type adhesive composite sheet 11...Base material 13...Film-type adhesive, 13a...First side of film-type adhesive

Claims

1. A film-like adhesive for cutting by plasma irradiation, The aforementioned film-like adhesive has energy ray curing properties. A film-like adhesive having a tack reduction rate X of 0.12 or higher; The aforementioned tack reduction rate X is a value expressed by the following formula (1): X=(Tb-Ta) / Tb (1) Tb is gas species O ２ This is the probe tack value at 23°C after performing the operation of irradiating the film-like adhesive with plasma for 1 minute for 15 times under the conditions of a flow rate of 100 mL / min and an output of 300 W. Ta is gas species O ２ The film-like adhesive was subjected to plasma irradiation 15 times for 1 minute under conditions of a flow rate of 100 mL / min and an output of 300 W. Subsequently, under a nitrogen gas atmosphere, the irradiance was set to 220 mW / cm². ２ , light intensity 190mJ / cm ２ This is the probe tack value at 23°C after irradiation with ultraviolet light under the specified conditions.

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

3. The film-like adhesive according to claim 1 or 2, wherein energy rays are irradiated after the plasma has been irradiated.

4. The film-like adhesive according to claim 1 or 2, wherein the ratio of the content of antioxidant (j1) to the total mass of the film-like adhesive is 0.1 to 5% by mass.

5. The device comprises a support sheet and a film-like adhesive provided on one surface of the support sheet, A film-like adhesive composite sheet wherein the film-like adhesive is the film-like adhesive described in claim 1.

6. The film-like adhesive composite sheet according to claim 5, wherein the support sheet consists only of a base material.

7. For the aforementioned film-like adhesive composite sheet, the illuminance was 230 mW / cm². ２ , light intensity 190mJ / cm ２ A test piece (T3) with a width of 25 mm was prepared by irradiating the film-like adhesive with ultraviolet light under the specified conditions to cure it with ultraviolet light. In the test specimen (T3), the support sheet is peeled off from the UV-cured film-like adhesive, and the angle between the surface of the UV-cured film to which the support sheet was attached and the surface of the support sheet to which the UV-cured film was attached is set to 180°. When a peel test is performed in which the support sheet is peeled off from the UV-cured film-like adhesive in its longitudinal direction at a peel speed of 300 mm / min, the peel force between the UV-cured film-like adhesive and the support sheet is 100 mN / 25 mm or less, as described in claim 5 or 6.

8. A method for manufacturing a chip with an adhesive cured product using the film-like adhesive composite sheet described in claim 5 or 6, The aforementioned adhesive-cured tip comprises a tip and an energy-ray cured film-like adhesive provided on one side of the tip. The manufacturing method for producing a chip with an adhesive-cured material, comprising: attaching the film-like adhesive in the film-like adhesive composite sheet to one side of a wafer; irradiating the wafer and the film-like adhesive with plasma to divide the wafer and produce a chip; cutting the film-like adhesive; and curing the cut film-like adhesive with energy rays to produce a chip with an adhesive-cured material; and then pulling the chip with the adhesive-cured material away from the support sheet and picking it up.

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