Film adhesive, dicing and die-bonding two-in-one film, semiconductor device, and manufacturing method for same

Abstract

Disclosed is a film adhesive containing a thermosetting resin component and an elastomer. The elastomer contains a (meth)acrylate polymer containing a structural unit derived from a (meth)acrylate having an epoxy group. The (meth)acrylate polymer satisfies at least one of the following conditions A-C. (Condition A) The content of structural units derived from a (meth)acrylate having an epoxy group is 6 mass% or more based on the total structural units of the (meth)acrylate polymer. (Condition B) The epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more. (Condition C) In an infrared absorption spectrum of the (meth)acrylate polymer, P(A) and P(B) satisfy the conditions of formula (1), where P(A) is the area of an absorption peak derived from the antisymmetric stretching of epoxy groups, and P(B) is the area of an absorption peak derived from the stretching vibration of carbonyl groups.　Formula 1: P(A) / P(B) ≥ 0.0055

Description

Film-like adhesive, dicing and die bonding integrated film, semiconductor device and method for manufacturing the same.

[0001] This disclosure relates to a film-like adhesive, a dicing-die bonding integrated film, and a semiconductor device and a method for manufacturing the same.

[0002] In recent years, stacked MCPs (Multi-Chip Packages), which consist of multiple semiconductor chips stacked in layers, have become widespread and are being incorporated as semiconductor devices (semiconductor packages) for semiconductor memory in mobile phones and portable audio devices. Furthermore, with the increasing multi-functionality of mobile phones and other devices, there is a growing demand for higher speed, higher density, and higher integration of semiconductor devices.

[0003] A commonly used method for manufacturing semiconductor devices involves attaching a dicing-die bonding integrated film, comprising an adhesive layer and a tack layer, to the back surface of a semiconductor wafer, and then cutting a portion of the semiconductor wafer, adhesive layer, and tack layer to create individual pieces (semiconductor wafer back surface attachment method). For example, Patent Documents 1 and 2 disclose a film-like adhesive used in the adhesive layer of this method. Such film-like adhesives typically contain a thermosetting resin component and a (meth)acrylate polymer as constituent components.

[0004] International Publication No. 2013 / 133275, International Publication No. 2020 / 013250

[0005] In stacked MCPs, semiconductor chips are stacked in multiple layers, so the film adhesive used in the dicing and die bonding integrated film is required to have sufficient elongation at break even when forming a thin film (for example, with a thickness of 15 μm or less). When the film adhesive has sufficient elongation at break, it tends to have excellent processability when forming a thin film (for example, the ability to cut the film for circular die-cutting).

[0006] In addition, in recent semiconductor devices, semiconductor chips composed of a circuit layer and a semiconductor layer tend to have thicker circuit layers and thinner semiconductor layers. In such semiconductor devices, chip cracks may occur during wire bonding, for example, when connecting the circuit layer of the semiconductor chip to the electrodes of the support member with bonding wires. Such chip cracks are presumed to occur because the semiconductor layer becomes thinner and more brittle, and is caused by vibrations during wire bonding. Therefore, film-like adhesives used in dicing and die bonding integrated films are required to have excellent wire bonding properties, such as being able to suppress chip cracks caused by vibrations during wire bonding when the film-like adhesive is cured.

[0007] The primary objective of this disclosure is to provide a film-like adhesive that has good processability and excellent wire bonding properties.

[0008] This disclosure provides a film-like adhesive described in [1] to [5], a dicing-die bonding integrated film described in [6], a semiconductor device described in [7], and a method for manufacturing a semiconductor device described in [8] to

[12] . [1] A film-like adhesive comprising a thermosetting resin component and an elastomer, wherein the elastomer comprises a (meth)acrylate polymer containing structural units derived from (meth)acrylate having epoxy groups, and the (meth)acrylate polymer satisfies at least one of the following conditions: (Condition A) The content of structural units derived from (meth)acrylate having epoxy groups is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer. (Condition B) The epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more. (Condition C) In the infrared absorption spectrum of the (meth)acrylate polymer, when P(A) is the area of ​​the absorption peak originating from the antisymmetric stretching of the epoxy group and P(B) is the area of ​​the absorption peak originating from the stretching vibration of the carbonyl group, P(A) and P(B) satisfy the condition of the following formula (1). P(A) / P(B) ≥ 0.0055 (1) [2] The film-like adhesive according to [1], which may further contain an inorganic filler, wherein the content of the inorganic filler is 0 to 5% by mass based on the total amount of the film-like adhesive. [3] The film-like adhesive according to [1], wherein the content of the elastomer is 30% by mass or more based on the total amount of the film-like adhesive. [4] The film-like adhesive according to [2], wherein the content of the elastomer is 30% by mass or more based on the total amount of the film-like adhesive. [5] The film-like adhesive according to any one of [1] to [4], which has a thickness of 15 μm or less. [6] A dicing-die bonding integrated film comprising, in this order, a base layer, an adhesive layer, and an adhesive layer made of a film-like adhesive according to any one of [1] to [5]. [7] A semiconductor device comprising: a semiconductor chip; a support member on which the semiconductor chip is mounted; and a cured product of a film-like adhesive according to any one of [1] to [5] provided between the semiconductor chip and the support member to bond the semiconductor chip and the support member.A method for manufacturing a semiconductor device, comprising: [8] A step of attaching the adhesive layer of the dicing-die bonding integrated film described in [6] to a semiconductor wafer; a step of producing a plurality of individualized semiconductor chips with adhesive pieces by cutting the semiconductor wafer to which the adhesive layer has been attached; and a step of bonding a first semiconductor chip with adhesive pieces, which has a first semiconductor chip and a first adhesive piece, to a support member via the first adhesive piece. [9] A method for manufacturing a semiconductor device according to [8], further comprising: a step of thermally curing the first adhesive piece on the first semiconductor chip with adhesive pieces at a temperature of 100 to 180°C for 15 to 60 minutes; and a step of electrically connecting the first semiconductor chip and the support member with a bonding wire.

[10] A method for manufacturing a semiconductor device according to [8], further comprising the step of bonding a second semiconductor chip having a second semiconductor chip and a second adhesive piece, from among the plurality of individualized semiconductor chips with adhesive pieces, to the surface of the first semiconductor chip with the first adhesive piece bonded to the support member, via the second adhesive piece.

[11] A method for manufacturing a semiconductor device according to

[10] , further comprising the steps of thermal curing the first adhesive piece in the first semiconductor chip with the first adhesive piece and the second adhesive piece in the second semiconductor chip with the second adhesive piece at a temperature of 100 to 180°C for 15 to 60 minutes, and electrically connecting the first semiconductor chip and the second semiconductor chip to the support member with a bonding wire.

[12] A method for manufacturing a semiconductor device, comprising the step of interposing a film-like adhesive described in any of [1] to [5] between a first semiconductor chip and a support member, or between a first semiconductor chip and a second semiconductor chip different from the first semiconductor chip, to bond the first semiconductor chip and the support member, or the first semiconductor chip and the second semiconductor chip.

[0009] This disclosure provides a film-like adhesive that has good processability and excellent wire bonding properties. Furthermore, this disclosure provides a dicing-die bonding integrated film using such a film-like adhesive, as well as a semiconductor device and a method for manufacturing the same. Finally, this disclosure provides a method for manufacturing a semiconductor device using such a dicing-die bonding integrated film.

[0010] Figure 1 is a schematic cross-sectional view showing one embodiment of a film-like adhesive. Figure 2 is a schematic cross-sectional view showing one embodiment of a dicing-die bonding integrated film. Figure 3 is a schematic cross-sectional view showing one embodiment of a semiconductor device. Figure 4 is a schematic cross-sectional view showing another embodiment of a semiconductor device. Figure 5 is a schematic cross-sectional view showing yet another embodiment of a semiconductor device.

[0011] Embodiments of the present disclosure will be described below with reference to the drawings as appropriate. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including steps, etc.) are not essential unless otherwise specified. The sizes of the components in each figure are conceptual, and the relative relationships of the sizes of the components are not limited to those shown in each figure.

[0012] The same applies to numerical values ​​and their ranges in this disclosure, and these do not limit this disclosure. Numerical ranges indicated using “~” in this specification indicate a range that includes the numerical values ​​before and after “~” as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another stepwise described numerical range. Also, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. Furthermore, the upper and lower limits stated individually can be combined in any way. Also, “A or B” means that either A or B is included, or both are included. Furthermore, unless otherwise specified, the materials exemplified below may be used individually or in combination of two or more. The content of each component in the composition means the total amount of multiple substances present in the composition if there are multiple substances corresponding to each component in the composition, unless otherwise specified.

[0013] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl group and (meth)acrylate polymer.

[0014] [Film-like adhesive] Figure 1 is a schematic cross-sectional view showing one embodiment of a film-like adhesive. The film-like adhesive 1 shown in Figure 1 may be thermosetting and may undergo a semi-cured (B-stage) state before reaching a fully cured (C-stage) state after curing treatment. The film-like adhesive 1 may be a die bonding film used for bonding a semiconductor chip to a support member, or for bonding semiconductor chips to each other. Since the film-like adhesive 1 contains a (meth)acrylate polymer as an elastomer that can provide excellent wire bonding properties, it can be suitably used for bonding semiconductor chips to each other.

[0015] The film-like adhesive 1 contains a thermosetting resin component (hereinafter sometimes referred to as "component (A)") and an elastomer (hereinafter sometimes referred to as "component (B)"). Component (B) contains a (meth)acrylate polymer (hereinafter sometimes referred to as "component (B1)") which includes structural units derived from (meth)acrylate having epoxy groups. In addition to components (A) and (B), the film-like adhesive 1 may further contain an inorganic filler (hereinafter sometimes referred to as "component (C)"), a coupling agent (hereinafter sometimes referred to as "component (D)"), a curing accelerator (hereinafter sometimes referred to as "component (E)"), and other components.

[0016] Component (A) may include, for example, an epoxy resin (hereinafter sometimes referred to as "component (A1)") and a phenolic resin (hereinafter sometimes referred to as "component (A2)").

[0017] (A) component: thermosetting resin component; (A1) component: epoxy resin. Component (A1) can be used without particular limitations as long as it has an epoxy group in its molecule. Examples of component (A1) include bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; phenol novolac type epoxy resin; cresol novolac type epoxy resin; bisphenol A novolac type epoxy resin; bisphenol F novolac type epoxy resin; stilbene type epoxy resin; triazine skeleton-containing epoxy resin; fluorene skeleton-containing epoxy resin; triphenolmethane type epoxy resin; biphenyl type epoxy resin; xylylene type epoxy resin; biphenyl aralkyl type epoxy resin; naphthalene type epoxy resin; and diglycidyl ether compounds of polycyclic aromatics such as polyfunctional phenols and anthracenes. Among these, component (A1) may include cresol novolac type epoxy resin, bisphenol F type epoxy resin, or bisphenol A type epoxy resin from the viewpoint of the film's tackiness, flexibility, etc. Bisphenol F type epoxy resins, for example, often have a relatively low softening point, with many having a softening point of 40°C or below.

[0018] Component (A1) may include a liquid epoxy resin (hereinafter sometimes referred to as "component (A1a)") having a softening point of 40°C or lower (for example, being liquid at 30°C). Component (A1) may be a combination of component (A1a) and a solid epoxy resin (hereinafter sometimes referred to as "component (A1b)") having a softening point exceeding 40°C (for example, being solid at 30°C). Component (A1) tends to more easily improve the storage modulus after curing by including component (A1a). Furthermore, component (A1) being a combination of component (A1a) and component (A1b) tends to make it easier to achieve thin films.

[0019] The softening point of component (A1) can be measured, for example, by the ring-and-ball method in accordance with JIS K7234:1986. Alternatively, the softening point of component (A1) may be taken from, for example, the manufacturer's catalog value.

[0020] Examples of commercially available products of component (A1a) include EXA-830CRP (product name, manufactured by DIC Corporation, liquid at 30°C), YDF-8170C (product name, manufactured by Nippon Steel Chemical & Material Co., Ltd., liquid at 30°C), and EP-4088S (product name, manufactured by ADEKA Corporation, liquid at 30°C).

[0021] Examples of commercially available components of (A1b) include YDCN-700-10 (product name, manufactured by Nippon Steel Chemical & Material Co., Ltd., cresol novolac type epoxy resin, epoxy equivalent: 210 g / eq, softening point: 80°C), N-500P-10 (product name, manufactured by DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent: 204 g / eq, softening point: 84°C), HP-4710 (product name, manufactured by DIC Corporation, naphthalene type epoxy resin, epoxy equivalent: 170 g / eq, softening point: 95°C), and NC-7000L (product name, manufactured by Nippon Kayaku Co., Ltd., naphthalene type epoxy resin, epoxy equivalent: 230 g / eq, softening point: 88°C).

[0022] When component (A1) is a combination of component (A1a) and component (A1b), the content of component (A1a) may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and may be 60% by mass or less, 50% by mass or less, or 40% by mass or less, based on the total amount of component (A1). The content of component (A1a) in component (A1) in the adhesive composition when forming a film-like adhesive may be the same as the above range.

[0023] When component (A1) is a combination of component (A1a) and component (A1b), the content of component (A1b) may be 40% by mass or more, 50% by mass or more, or 60% by mass or more, and may be 95% by mass or less, 90% by mass or less, or 85% by mass or less, based on the total amount of component (A1). The content of component (A1b) in component (A1) in the adhesive composition when forming a film-like adhesive may be the same as the above range.

[0024] The epoxy equivalent of component (A1) is not particularly limited, but may be 80 to 350 g / eq or 100 to 300 g / eq. When the epoxy equivalent of component (A1) is within this range, it tends to be easier to maintain the bulk strength of the film-like adhesive while ensuring the fluidity of the adhesive composition when forming the film-like adhesive. The epoxy equivalent of component (A1) can be measured, for example, by potentiometric titration in accordance with JIS K7236:2009. Alternatively, the epoxy equivalent of component (A1) may be taken from, for example, the catalog value of the supplier.

[0025] • Component (A2): Phenolic resin. Component (A2) acts as a curing agent for component (A1), i.e., it can be a curing agent for epoxy resin. By containing component (A2) in the film adhesive, the film adhesive can be crosslinked at high density, improving the storage modulus after curing.

[0026] Component (A2) can be used without particular limitations as long as it has a phenolic hydroxyl group in its molecule. Examples of component (A2) include novolac-type phenolic resins obtained by condensing or co-condensing phenols such as phenol, cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene with compounds having an aldehyde group such as formaldehyde under an acidic catalyst; phenolic aralkyl resins synthesized from phenols such as allylated bisphenol A, allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenol and / or naphthols with dimethoxyp-xylene or bis(methoxymethyl)biphenyl; naphthol aralkyl resins; biphenyl aralkyl-type phenolic resins; and phenyl aralkyl-type phenolic resins. Among these, component (A2) may include novolac-type phenolic resin or phenyl aralkyl-type phenolic resin.

[0027] The hydroxyl group equivalent of component (A2) may be 70 to 300 g / eq or 90 to 280 g / eq. When the hydroxyl group equivalent of component (A2) is 70 g / eq or more, it is possible to prevent problems caused by foaming, outgassing, etc., and when it is 300 g / eq or less, the storage modulus tends to improve further. The hydroxyl group equivalent of component (A2) can be measured by titration using, for example, the acetylation method with acetic anhydride. Alternatively, the hydroxyl group equivalent of component (A2) may be taken from, for example, the catalog value of the distributor.

[0028] (A2) The softening point of component (A2) is not particularly limited, but may be, for example, 90°C or higher, 100°C or higher, or 110°C or higher. The upper limit of the softening point of component (A2) may be, for example, 200°C or lower. The softening point of component (A2) can be measured, for example, by the ring-and-ball method in accordance with JIS K6910:2007. The softening point of component (A2) may be, for example, the value in the manufacturer's catalog.

[0029] (A2) Examples of commercially available components include PSM-4326 (trade name, manufactured by Gun-ei Chemical Industry Co., Ltd., softening point: 120°C), J-DPP-140 (trade name, manufactured by JFE Chemical Corporation, softening point: 140°C), and GPH-103 (trade name, manufactured by Nippon Kayaku Co., Ltd., softening point: 103°C).

[0030] The equivalent ratio (epoxy groups / hydroxyl groups) of the number of epoxy groups in component (A1) to the number of hydroxyl groups in component (A2) may be 0.30 / 0.70 to 0.70 / 0.30, 0.35 / 0.65 to 0.65 / 0.35, 0.40 / 0.60 to 0.60 / 0.40, or 0.45 / 0.55 to 0.55 / 0.45 from the viewpoint of curability. When the equivalent ratio is 0.30 / 0.70 or higher, more sufficient curability tends to be obtained. When the equivalent ratio is 0.70 / 0.30 or lower, it is possible to prevent the viscosity from becoming too high and to obtain more sufficient fluidity.

[0031] The content of component (A1) (the sum of components (A1a) and (A1b)) may be 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more, based on the total amount of the film-like adhesive. When the content of component (A1) is within this range, it tends to be easier to improve the storage modulus after curing. From the viewpoint of ease of handling, the content of component (A1) may be 60% by mass or less, 55% by mass or less, 50% by mass or less, or 45% by mass or less, based on the total amount of the film-like adhesive. The content of component (A1) (the sum of components (A1a) and (A1b)) in the adhesive composition when forming the film-like adhesive may be the same as the above range.

[0032] The content of component (A2) may be 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, based on the total amount of the film-like adhesive. When the content of component (A2) is within this range, it tends to be easier to improve the storage modulus after curing. From the viewpoint of handling, the content of component (A2) may be 40% by mass or less, 35% by mass or less, or 30% by mass or less, based on the total amount of the film-like adhesive. The content of component (A2) in the adhesive composition when forming the film-like adhesive may be the same as the above range.

[0033] The content of component (A) (the sum of components (A1) and (A2)) may be 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total amount of the film-like adhesive. When the content of component (A) is within this range, it tends to be easier to improve the storage modulus after curing. From the viewpoint of handling, the content of component (A) may be 80% by mass or less, 75% by mass or less, or 70% by mass or less, based on the total amount of the film-like adhesive. The content of component (A) (the sum of components (A1) and (A2)) in the adhesive composition when forming the film-like adhesive may be the same as the above range.

[0034] (B) Component: Elastomer Component (B) is an elastomer (a resin with rubber-like elasticity). Component (B) contains component (B1). The inclusion of component (B1) in component (B) provides good processability to the film-like adhesive and excellent wire bonding properties.

[0035] Component (B1) is a (meth)acrylate polymer containing structural units derived from (meth)acrylate having an epoxy group. Examples of compounds that provide structural units derived from (meth)acrylate having an epoxy group include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, the compound that provides structural units derived from (meth)acrylate having an epoxy group may be glycidyl (meth)acrylate or glycidyl methacrylate.

[0036] Component (B1) satisfies at least one of conditions A, B, and C. Component (B1) may satisfy at least two of conditions A, B, and C, or it may satisfy all of conditions A, B, and C. (Condition A) The content of structural units derived from (meth)acrylate having epoxy groups is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer. (Condition B) The epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more. (Condition C) In the infrared absorption spectrum of the (meth)acrylate polymer, when P(A) is the area of ​​the absorption peak derived from the antisymmetric stretching of the epoxy group and P(B) is the area of ​​the absorption peak derived from the stretching vibration of the carbonyl group, P(A) and P(B) satisfy the condition of the following formula (1): P(A) / P(B) ≥ 0.0055 (1)

[0037] (Condition A) The content of structural units derived from (meth)acrylate having epoxy groups is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer. When the content of structural units derived from (meth)acrylate having epoxy groups is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer, it is possible to impart good processability and excellent wire bonding properties when applied to a film-like adhesive. The content of structural units derived from (meth)acrylate having epoxy groups may be 8% by mass or more, 10% by mass or more, 12% by mass or more, 14% by mass or more, 16% by mass or more, 18% by mass or more, 20% by mass or more, or 22% by mass or more, based on the total structural units of the (meth)acrylate polymer, and may be 30% by mass or less, 28% by mass or less, 26% by mass or less, 24% by mass or less, 22% by mass or less, 20% by mass or less, 18% by mass or less, 16% by mass or less, or 14% by mass or less.

[0038] In this specification, the content of each structural unit in the polymer means the ratio of the charged mass of the monomer corresponding to each structural unit to the total amount of the monomers used in the polymerization. The content of the structural unit derived from the (meth)acrylate having an epoxy group can be calculated, for example, from the charged amount of the monomers used in the production of the (meth)acrylate polymer.

[0039] (Condition B) The epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more. When the epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more, good processability can be imparted when applied to a film adhesive, and excellent wire bonding property can be imparted. The epoxy value of the (meth)acrylate polymer may be 0.42 eq / kg or more, 0.50 eq / kg or more, 0.55 eq / kg or more, 0.60 eq / kg or more, 0.65 eq / kg or more, 0.70 eq / kg or more, 0.75 eq / kg or more, 0.80 eq / kg or more, 0.85 eq / kg or more, 0.90 eq / kg or more, 0.95 eq / kg or more, 1.00 eq / kg or more, 1.05 eq / kg or more, or 1.10 eq / kg or more, and may be 2.00 eq / kg or less, 1.80 eq / kg or less, 1.60 eq / kg or less, 1.40 eq / kg or less, 1.20 eq / kg or less, 1.10 eq / kg or less, 1.00 eq / kg or less, 0.90 eq / kg or less, 0.80 eq / kg or less, or 0.70 eq / kg or less.

[0040] In this specification, the epoxy value (epoxy index) means the number of equivalents of epoxy groups contained in 1 kg of the (meth)acrylate polymer. The epoxy value (epoxy index) is a value measured by an indicator titration method in accordance with JIS K7236:2009.

[0041] (Condition C) In the infrared absorption spectrum of the (meth)acrylate polymer, when the area of the absorption peak derived from the antisymmetric stretching of the epoxy group is P(A) and the area of the absorption peak derived from the stretching vibration of the carbonyl group is P(B), P(A) and P(B) satisfy the conditions of the following formula (1). P(A) / P(B) ≥ 0.0055 (1)

[0042] P(A) / P(B) is 0.0055 or more. When P(A) / P(B) is 0.0055 or more, good processability can be imparted when applied to a film adhesive, and excellent wire bonding property can be imparted. P(A) / P(B) may be 0.0060 or more, 0.0070 or more, 0.0080 or more, 0.0090 or more , 0.0100 or more, 0.0120 or more, 0 .0140 or more, 0 .0160 or more, 0 .0180 or more , or may be 0.0200 or more, or 0.0220 or more, and may be 0.0500 or less, 0.0450 or less, 0.0420 or less, 0.0400 or less, 0.0350 or less, 0.0300 or less, 0.0280 or less, 0.0260 or less, 0.0240 or less, 0.0220 or less, 0.0200 or less, 0.0180 or less, 0.0160 or less, 0.0140 or less, 0.0120 or less, or 0.0110 or less.

[0043] The epoxy group is mainly derived from (meth)acrylate having an epoxy group as a structural unit, and the carbonyl group is mainly derived from (meth)acrylate as a structural unit. That is, P(A) / P(B) means the ratio of (meth)acrylate having an epoxy group to the total amount of (meth)acrylate in the (meth)acrylate polymer. The area of the absorption peak (P(A)) derived from the antisymmetric stretching of the epoxy group and the area of the absorption peak (P(B)) derived from the stretching vibration of the carbonyl group can be calculated by, for example, the following method.

[0044] First, for the (meth)acrylate polymer, a total reflection IR spectrum is obtained by the ATR method (total reflection measurement method). For IR measurement, for example, LUMOS II (manufactured by Bruker, ATR crystal: germanium, detector: MCT, infrared incident angle: 30°) can be used. The IR measurement of the (meth)acrylate polymer is performed after background measurement, and atmospheric correction is performed on the obtained spectrum. Next, the spectrum is displayed with the absorbance on the vertical axis and the wave number (cm －１ ) on the horizontal axis, and in the displayed spectrum, 880 cm －１ and 927 cm －１Determine the wavenumbers of two points corresponding to the minimum absorbance within the specified range. The straight line connecting these two points on the spectrum is defined as the baseline. The area of ​​absorbance enclosed by the spectrum and the baseline is defined as the area of ​​the absorption peak (P(A)) originating from the antisymmetric stretching of the epoxy group. (1661 cm⁻¹ on the spectrum) －１ and 1842 cm －１ The straight line connecting these two points is defined as the baseline, and the area of ​​absorbance enclosed by the spectrum and the baseline is defined as the area of ​​the absorption peak originating from the stretching vibration of the carbonyl group (P(B)). Based on P(A) and P(B) defined in this way, P(A) / P(B) can be calculated.

[0045] The epoxy value under condition B and the P(A) / P(B) under condition C can also be determined by extracting the (meth)acrylate polymer from the film-like adhesive described below and obtaining the extracted (meth)acrylate polymer. Methods for extracting the (meth)acrylate polymer from the film-like adhesive include, for example, Method 1 and Method 2. ・Method 1 (When the film-like adhesive is completely soluble in tetrahydrofuran (THF)) The film-like adhesive is dissolved in THF, and the (meth)acrylate polymer is separated and recovered based on molecular size (molecular weight) by preparative gel permeation chromatography (preparative GPC). ・Method 2 (When the film-like adhesive is not completely soluble in tetrahydrofuran (THF)) The film-like adhesive is thoroughly washed with acetonitrile to elute components other than the (meth)acrylate polymer from the film-like adhesive, and the (meth)acrylate polymer is recovered.

[0046] The (meth)acrylate polymer may further contain structural units derived from (meth)acrylates other than those having epoxy groups, in addition to structural units derived from (meth)acrylates having epoxy groups.

[0047] Other compounds that provide structural units derived from (meth)acrylate may be (meth)acrylates having one (meth)acryloyl group. Examples of other (meth)acrylates include (meth)acrylic acid; (meth)acrylamide; (meth)acryloylmorpholine; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Alkyl (meth)acrylates having alkyl groups with 1 to 18 carbon atoms, such as isodecyl (meth)acrylate, dodecyl (meth)acrylate (n-lauryl (meth)acrylate), isomiristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; alkenyl (meth)acrylates having alkenyl groups with 2 to 18 carbon atoms, such as 3-butenyl (meth)acrylate; aromatic rings such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate (Meth)acrylates having alicyclic groups; methoxytetraethylene glycol (meth)acrylate, methoxyhexaethylene glycol (meth)acrylate, methoxyoctaethylene glycol (meth)acrylate, methoxynononaethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxyheptapropylene glycol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, etc.; (meth)acrylates having alicyclic groups such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; (meth)acrylates having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate;Examples include (meth)acrylamide derivatives such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and N-hydroxyethyl (meth)acrylamide; (meth)acrylonitriles such as acrylonitrile and methacrylonitrile; polyalkylene glycol mono(meth)acrylates such as tetraethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, octapropylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, and tripropylene glycol mono(meth)acrylate; and (meth)acrylates having a siloxane skeleton. Among these, other (meth)acrylates may include at least one selected from the group consisting of alkyl (meth)acrylates and (meth)acrylonitriles. The alkyl (meth)acrylate may be an alkyl (meth)acrylate having an alkyl group with 1 to 6 carbon atoms. The (meth)acrylonitrile may be acrylonitrile.

[0048] The content of other structural units derived from (meth)acrylate may be 70% by mass or more, 72% by mass or more, 74% by mass or more, 76% by mass or more, 78% by mass or more, 80% by mass or more, 82% by mass or more, 84% by mass or more, or 86% by mass or more, based on the total structural units of the (meth)acrylate polymer, and may be 94% by mass or less, 92% by mass or less, 90% by mass or less, 88% by mass or less, 86% by mass or less, 84% by mass or less, 82% by mass or less, 80% by mass or less, or 78% by mass or less.

[0049] The (meth)acrylate polymer may further contain structural units derived from copolymer monomers copolymerizable with (meth)acrylate, in addition to structural units derived from epoxy group-containing (meth)acrylate and other structural units derived from (meth)acrylate. Examples of compounds that provide structural units derived from copolymer monomers include styrene, 4-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, cyclohexylmaleimide, phenylmaleimide, and maleic anhydride. The content of copolymer monomers may be 0 to 30% by mass, 0 to 20% by mass, 0 to 10% by mass, or 0 to 5% by mass, based on the total structural units of the (meth)acrylate polymer.

[0050] In one embodiment, the (meth)acrylate polymer may contain structural units derived from epoxy group-containing (meth)acrylate, structural units derived from alkyl (meth)acrylate, and structural units derived from (meth)acrylonitrile. In one embodiment, the (meth)acrylate polymer may be composed of these structural units.

[0051] The weight-average molecular weight (Mw) of the (meth)acrylate polymer may be between 200,000 and 2,000,000. When the weight-average molecular weight (Mw) of the (meth)acrylate polymer is within this range, the effects of this disclosure tend to be more easily obtained, allowing for appropriate control of film formation properties, film strength, flexibility, tackiness, etc., as well as excellent reflowability and improved embedding properties. The weight-average molecular weight (Mw) of the (meth)acrylate polymer may be 300,000 or more, 400,000 or more, 500,000 or more, or 550,000 or more, and may be 1,800,000 or less, 1,500,000 or less, 1,300,000 or less, or 1,100,000 or less.

[0052] In this specification, weight-average molecular weight (Mw) refers to the value obtained by measuring by gel permeation chromatography (GPC) and converting it using a calibration curve with standard polystyrene. If multiple peaks are observed in the GPC, the weight-average molecular weight attributable to the peak with the highest intensity is defined as the weight-average molecular weight in this specification.

[0053] (Meth)acrylate polymers can be obtained by known methods of synthesis. Examples of synthesis methods include solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, precipitation polymerization, gas-phase polymerization, plasma polymerization, and supercritical polymerization. Examples of polymerization reactions include radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization (ATRP (atomic transfer radical polymerization), RAFT (reversible addition-cleavage chain transfer polymerization), etc.), living cationic polymerization, living anionic polymerization, coordination polymerization, and immortal polymerization. Among these, synthesis by radical polymerization using solution polymerization has advantages such as cost-effectiveness, high reaction rate, ease of polymerization control, and the ability to directly use the resin solution obtained by polymerization in formulations.

[0054] Here, we will describe a method for producing (meth)acrylate polymers by radical polymerization using solution polymerization.

[0055] In one embodiment, a (meth)acrylate polymer can be obtained by a method comprising the step of polymerizing a (meth)acrylate having an epoxy group, and optionally a monomer containing other (meth)acrylates and copolymer monomers.

[0056] To obtain such (meth)acrylate polymers, known radical polymerization initiators can be used. Examples of radical polymerization initiators include azo polymerization initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis(2,4,4-trimethylpentane), and dimethyl-2,2'-azobis(2-methylpropionate); and peroxide polymerization initiators such as benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and 1,1-bis(t-butylperoxy)cyclododecane.

[0057] The amount of radical polymerization initiator used may be 0.01 to 5 parts by mass, 0.02 to 4 parts by mass, or 0.03 to 3 parts by mass per 100 parts by mass of the total monomers.

[0058] The solvent used in solution polymerization is not particularly limited as long as it is a solvent capable of dissolving the (meth)acrylate polymer. Examples of solvents include known organic solvents such as esters like ethyl acetate, propyl acetate, and butyl acetate; aromatic hydrocarbons like toluene, xylene, and benzene; aliphatic hydrocarbons like hexane and heptane; alicyclic hydrocarbons like cyclohexane and methylcyclohexane; ketones like methyl ethyl ketone and methyl isobutyl ketone; glycols like ethylene glycol, propylene glycol, and dipropylene glycol; glycol ethers like methyl cellosolve, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; and glycol esters like ethylene glycol diacetate and propylene glycol monomethyl ether acetate. Furthermore, polymerization can also be carried out using supercritical carbon dioxide or the like as a solvent.

[0059] The reaction temperature can be set appropriately depending on the type of radical polymerization initiator used. For example, the reaction temperature may be 40 to 125°C or 60 to 120°C. The reaction time can also be set appropriately depending on the type of radical polymerization initiator used. For example, the reaction time may be 1 to 24 hours or 3 to 15 hours.

[0060] Component (B) may further contain, in addition to component (B1), an elastomer other than component (B1) (hereinafter sometimes referred to as "component (B2)"). Examples of component (B2) include (meth)acrylate polymers other than component (B1) (including (meth)acrylic rubber), urethane resins (including urethane rubber), silicone resins (including silicone rubber), styrene-based elastomers, etc. Examples of component (B2) include polymers having organopolysiloxanes in their side chains.

[0061] The weight-average molecular weight (Mw) of component (B2) may be 100,000 or more, 300,000 or more, or 500,000 or more, and may be 3,000,000 or less, 2,000,000 or less, or 1,000,000 or less.

[0062] The content of component (B1) may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more, or 100% by mass, based on the total amount of component (B). The content of component (B1) in component (B) in the adhesive composition when forming a film-like adhesive may be the same as the above range.

[0063] The content of component (B2) may be 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, or 5% by mass or less, based on the total amount of component (B), and may also be 0% by mass. The content of component (B2) in component (B) in the adhesive composition when forming a film-like adhesive may be the same as the above range.

[0064] The content of component (B) may be 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, based on the total amount of the film-like adhesive. When the content of component (B) is within this range, it tends to have excellent thin-film formation properties, excellent break elongation when a thin film is formed, and the warping of semiconductor devices (semiconductor packages) can be suppressed. The content of component (B) may be 60% by mass or less, 55% by mass or less, 50% by mass or less, or 45% by mass or less, based on the total amount of the film-like adhesive. When the content of component (B) is within this range, it tends to be easier to further improve the storage modulus after curing. The content of component (B) in the adhesive composition when forming the film-like adhesive may be the same as the above range.

[0065] (C) Component: The inorganic filler film adhesive 1 may further contain component (C), or it may not contain component (C). In other words, the film adhesive 1 may exist in an embodiment that contains component (C) and an embodiment that substantially does not contain component (C).

[0066] Examples of component (C) include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, and silica. Among these, component (C) may be silica from the viewpoint of adjusting the melt viscosity. The shape of component (C) is not particularly limited, but it may be spherical.

[0067] The average particle size of component (C) may be 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less, from the viewpoint of fluidity and storage modulus. The average particle size of component (C) may be, for example, 0.01 μm or more. Here, the average particle size refers to the particle size with an integrated frequency of 50% in the particle size distribution determined by the laser diffraction / scattering method. The average particle size of component (C) can also be determined by using a film-like adhesive containing component (C). In this case, the residue obtained by heating the film-like adhesive to decompose the resin component is dispersed in a solvent to prepare a dispersion, and the average particle size of component (C) can be determined from the particle size distribution obtained by applying the laser diffraction / scattering method to this dispersion.

[0068] The content of component (C) may be 0 to 5% by mass based on the total amount of the film-like adhesive. When the content of component (C) is within this range, it tends to be possible to further thin films. Also, when the content of component (C) is within this range, the elongation at break when a thin film is formed is excellent, the processability is excellent, and the warping of semiconductor devices (semiconductor packages) tends to be suppressed. In one embodiment, the content of component (C) may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, or 0.1% by mass or less, based on the total amount of the film-like adhesive. In one embodiment, the content of component (C) may be 0% by mass based on the total amount of the film-like adhesive. That is, in one embodiment, the film-like adhesive may not contain component (C). In one embodiment, the content of component (C) may be 0% by mass or more, greater than 0% by mass, or 1% by mass or more, based on the total amount of the film-like adhesive. Furthermore, the content of component (C) in the adhesive composition when forming the film-like adhesive may be the same as the range described above.

[0069] Component (A) and component (B), or component (A), component (B), and component (C) may be the main components of the film-like adhesive of this embodiment. The total content of component (A) and component (B), or the total content of component (A), component (B), and component (C), may be, for example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 96% by mass or more, 97% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.7% by mass or more, or 99.9% by mass or more, based on the total amount of the film-like adhesive. The total content of component (A) and component (B), or the total content of component (A), component (B), and component (C), may be, for example, 100% by mass or less, 99.9% by mass or less, 99.7% by mass or less, or 99.5% by mass or less, based on the total amount of the film-like adhesive.

[0070] (D) Component: Coupling agent Component (D) may be a silane coupling agent. Examples of silane coupling agents include γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-(2-aminoethyl)aminopropyltrimethoxysilane.

[0071] (E) component: curing accelerator. Examples of (E) component include imidazoles and their derivatives, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, etc. Among these, from the viewpoint of reactivity, (E) may be imidazoles and their derivatives.

[0072] Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole.

[0073] Component (E) may contain 2-phenylimidazole because it readily promotes hardening at low temperatures.

[0074] The film-like adhesive may further contain other components. Examples of other components include pigments, ion capture agents, antioxidants, and so on.

[0075] The total content of component (D), component (E), and other components may be 0% by mass or more, 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, based on the total amount of the film-like adhesive, and may be 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less. The total content of component (D), component (E), and other components in the adhesive composition when forming the film-like adhesive may be the same as the above range.

[0076] The thickness of the film-like adhesive 1 may be 15 μm or less. The thickness of the film-like adhesive 1 may be 12 μm or less, 10 μm or less, 8 μm or less, 6 μm or less, 5 μm or less, 4 μm or less, or 3 μm or less. The thickness of the film-like adhesive 1 may be 0.1 μm or more, 0.3 μm or more, or 0.5 μm or more. The thickness of the film-like adhesive 1 can be determined, for example, by measuring the thickness at five arbitrary locations on a cross-section of the film-like adhesive 1 using a scanning electron microscope (SEM) image and calculating the average of the measured values.

[0077] When the film-like adhesive 1 is cured at 140°C for 30 minutes, the storage modulus of the cured product at 150°C may be 40 MPa or higher, and may be 45 MPa or higher, 50 MPa or higher, 55 MPa or higher, 60 MPa or higher, 65 MPa or higher, 70 MPa or higher, 75 MPa or higher, 80 MPa or higher, 85 MPa or higher, 90 MPa or higher, 95 MPa or higher, 100 MPa or higher, 105 MPa or higher, 110 MPa or higher, 115 MPa or higher, 120 MPa or higher, 125 MPa or higher, or 130 MPa or higher. When the storage modulus is 40 MPa or higher, it can compensate for the brittleness of semiconductor chips due to thinning, and as a result, it tends to suppress the occurrence of chip cracks and have excellent wire bonding properties. The upper limit of the storage modulus is not particularly limited, but may be, for example, 500 MPa or less, 300 MPa or less, 250 MPa or less, or 200 MPa or less.

[0078] In this specification, the storage modulus at 150°C of a cured product obtained by curing a film-like adhesive at 140°C for 30 minutes can be measured, for example, by the following method. Multiple layers of the film-like adhesive are laminated on a 70°C hot plate using a rubber roll to obtain a laminate with a thickness of 160 to 200 μm. The obtained laminate is cut to a size of 6 mm or more in width and 35 mm or more in length, and after curing the laminate at 140°C for 30 minutes, it is cut to a size of 4 mm in width and 33 mm in length to prepare a sample for measurement. The sample is mounted on a dynamic viscoelasticity measuring device (e.g., Rheogel-E4000, manufactured by UBM Co., Ltd.), and the dynamic viscoelasticity of the sample is measured under the following conditions. From the measurement results, the storage modulus at 150°C is read and taken as the storage modulus at 150°C of the film-like adhesive. (Conditions) ・Measurement mode: Tensile ・Chuck distance: 20 mm ・Heating rate: 10°C / min ・Frequency: 10 Hz ・Load: Automatic static load ・Measurement temperature: 30-270°C

[0079] The elongation at break of the film-like adhesive 1 at 25°C may be 300% or more, and may be 320% or more, 350% or more, 380% or more, 400% or more, 420% or more, 450% or more, 480% or more, 500% or more, 520% ​​or more, 550% or more, 580% or more, 600% or more, 620% or more, 650% or more, 680% or more, 700% or more, 720% or more, 750% or more, 780% or more, 800% or more, 820% or more, 850% or more, 880% or more, 900% or more, 920% or more, 950% or more, 980% or more, or 1000% or more. When the elongation at break is 300% or more, the processability when forming a thin film (for example, the ability to cut the film for circular die-cutting) tends to be excellent. There is no particular limit to the elongation at break, but it may be, for example, 2000% or less, 1500% or less, or 1200% or less.

[0080] In this specification, the elongation at break of a film-like adhesive at 25°C can be measured, for example, by the following method. A sample for measurement is prepared by punching out a dumbbell-shaped No. 1 tensile test specimen from a film-like adhesive (3 to 10 μm thick) in the B-stage state and removing the support film. The sample is mounted on a high-speed tensile testing machine (e.g., RTF-1250-HS-PL, A&D Company, Limited) using a jig to ensure that the distance between the chucks is maintained, and the measurement is performed under the following conditions. From the measurement results, the film length at the point where the film breaks is read, and the elongation at break of the film-like adhesive is calculated using formula (2). Breaking elongation (%) = [(gauge length after test (mm) - gauge length (mm)) / gauge length (mm)] × 100 ... (2) (Conditions) Load cell: 50N Distance between chucks: 100mm Gauge length: 40mm Tensile speed: 100mm / min Measurement temperature: 25℃

[0081] The film-like adhesive 1 shown in Figure 1 is formed by molding an adhesive composition containing component (A) and component (B), and optionally component (C) and additional components, into a film. Such a film-like adhesive 1 can be formed by applying the adhesive composition to a support film. In forming the film-like adhesive 1, a varnish (adhesive varnish) containing the adhesive composition and a solvent may also be used. When using an adhesive varnish, the adhesive varnish can be prepared by mixing or kneading component (A) and component (B), and optionally component (C) and additional components, in a solvent, applying the obtained adhesive varnish to a support film, and removing the solvent by heating and drying to obtain the film-like adhesive 1.

[0082] The support film is not particularly limited as long as it can withstand the above-mentioned heat drying, but may be, for example, polyester film, polypropylene film, polyethylene terephthalate film, polyimide film, polyetherimide film, polyethylene naphthalate film, polymethylpentene film, etc. The support film may be a multilayer film made by combining two or more types, and its surface may be treated with a release agent such as silicone or silica. The thickness of the support film may be, for example, 10 to 200 μm or 20 to 170 μm.

[0083] Mixing or kneading can be carried out using conventional agitators, dispersers, three-roll mills, ball mills, and other dispersers, in appropriate combinations.

[0084] The solvent used in the preparation of the adhesive varnish is not limited as long as it can uniformly dissolve, knead, or disperse each component, and conventionally known solvents can be used. Examples of such solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, as well as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, and xylene. From the viewpoint of drying speed and cost, the solvent may be methyl ethyl ketone or cyclohexanone.

[0085] Known methods can be used to apply the adhesive varnish to the support film, such as the knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, and curtain coating method. The heating and drying conditions are not particularly limited as long as the solvent used is sufficiently evaporated, but may be 50 to 150°C for 1 to 30 minutes.

[0086] Since the film-like adhesive 1 can be made into a thin film, it can be suitably used in the manufacturing process of stacked MCPs (for example, three-dimensional NAND memory), which are semiconductor devices formed by stacking multiple semiconductor chips.

[0087] [Dicing and Die Bonding Integrated Film] Figure 2 is a schematic cross-sectional view showing one embodiment of a dicing and die bonding integrated film. The dicing and die bonding integrated film 10 shown in Figure 2 comprises, in this order, a base layer 2, an adhesive layer 3, and an adhesive layer 1A made of the above-mentioned film-like adhesive 1. The base layer 2 and the adhesive layer 3 may be layers that constitute a dicing film 4. By using such a dicing and die bonding integrated film 10, the lamination process to the semiconductor wafer is reduced to one step, thus improving work efficiency. The dicing and die bonding integrated film may be in the form of a film, sheet, tape, etc.

[0088] The dicing film 4 comprises a base layer 2 and an adhesive layer 3 provided on the base layer 2.

[0089] Examples of the base layer 2 include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. These base layers 2 may be subjected to surface treatments such as primer application, UV treatment, corona discharge treatment, polishing treatment, and etching treatment as needed.

[0090] The adhesive layer 3 is a layer made of adhesive. The adhesive is not particularly limited as long as it has sufficient adhesive strength to prevent the semiconductor chip from scattering during the dicing process and low enough adhesive strength to avoid damaging the semiconductor chip during the subsequent semiconductor chip pickup process. Adhesives conventionally known in the field of dicing films can be used. The adhesive may be either radiation-curable or radiation-non-curable. The radiation may be, for example, ultraviolet light. A radiation-non-curable adhesive is an adhesive that exhibits a certain level of tackiness with short-term pressure. On the other hand, a radiation-curable adhesive is an adhesive that has the property of decreasing tackiness upon irradiation with radiation (for example, ultraviolet light).

[0091] The thickness of the dicing film 4 (base layer 2 and adhesive layer 3) may be 60 to 150 μm or 70 to 130 μm from the viewpoint of economy and ease of handling of the film.

[0092] The dicing-die bonding integrated film 10 can be obtained, for example, by preparing a film-like adhesive 1 and a dicing film 4, and bonding the film-like adhesive 1 and the adhesive layer 3 of the dicing film 4 together. Alternatively, the dicing-die bonding integrated film 10 can also be obtained, for example, by preparing a dicing film 4 and applying an adhesive composition (adhesive varnish) onto the adhesive layer 3 of the dicing film 4, similar to the method for forming the film-like adhesive 1 described above.

[0093] When bonding a film-like adhesive 1 to the adhesive layer 3 of a dicing film 4, the integrated dicing-die bonding film 10 can be formed by laminating the film-like adhesive 1 onto the dicing film 4 under predetermined conditions (for example, at room temperature (25°C) or in a heated state) using a roll laminator, vacuum laminator, etc. Since the integrated dicing-die bonding film 10 can be manufactured continuously and is highly efficient, it may also be formed using a roll laminator in a heated state.

[0094] The film-like adhesive and the dicing-die bonding integrated film may be used in the manufacturing process of semiconductor devices, and may be used in the manufacturing process of semiconductor devices comprising a plurality of semiconductor chips stacked on top of each other. The film-like adhesive and the dicing-die bonding integrated film may be used in the manufacturing process of semiconductor devices which includes the steps of: laminating the adhesive layer of the film-like adhesive or the dicing-die bonding integrated film onto a semiconductor wafer or a semiconductor chip that has already been separated into individual pieces, and obtaining a semiconductor chip with adhesive pieces by cutting with a rotating blade, laser or stretching; and bonding the semiconductor chip with adhesive pieces onto a support member or another semiconductor chip via adhesive pieces.

[0095] Film-type adhesives are also suitably used as adhesives for bonding semiconductor chips together in stacked MCPs (for example, three-dimensional NAND memory), which are semiconductor devices formed by stacking multiple semiconductor chips.

[0096] The film-like adhesive can also be used, for example, as a protective sheet to protect the back surface of a semiconductor chip in a flip-chip semiconductor device, or as a sealing sheet to seal the space between the surface of a semiconductor chip in a flip-chip semiconductor device and the adherend.

[0097] A semiconductor device manufactured using a film-like adhesive and a dicing / die bonding integrated film will be described in detail below with reference to the drawings. It should be noted that various structures of semiconductor devices have been proposed in recent years, and the applications of the film-like adhesive and dicing / die bonding integrated film of this embodiment are not limited to the semiconductor device with the structure described below.

[0098] [Semiconductor Device] Figure 3 is a schematic cross-sectional view showing one embodiment of a semiconductor device. The semiconductor device 100 shown in Figure 3 comprises a semiconductor chip 11 (first semiconductor chip), a support member 12 on which the semiconductor chip 11 is mounted, and an adhesive member 15. The adhesive member 15 is provided between the semiconductor chip 11 and the support member 12 and adheres the semiconductor chip 11 and the support member 12. The adhesive member 15 is a cured product of an adhesive composition (a cured product of a film-like adhesive). The connection terminals (not shown) of the semiconductor chip 11 are electrically connected to external connection terminals (not shown) via bonding wires 13, and the semiconductor chip 11 and the bonding wires 13 are sealed by a sealing material 14.

[0099] Figure 4 is a schematic cross-sectional view showing another embodiment of a semiconductor device. In the semiconductor device 110 shown in Figure 4, the first semiconductor chip 11a (first semiconductor chip) is bonded to a support member 12 on which terminals 16 are formed by an adhesive member 15a (cured product of an adhesive composition (cured product of a film-like adhesive)), and the second semiconductor chip 11b (second semiconductor chip) is further bonded to the first semiconductor chip 11a by an adhesive member 15b (cured product of an adhesive composition (cured product of a film-like adhesive)). The connection terminals (not shown) of the first semiconductor chip 11a and the second semiconductor chip 11b are electrically connected to an external connection terminal via a bonding wire 13, and the semiconductor chips 11a, 11b and the bonding wire 13 are sealed by a sealing material 14. The semiconductor device 110 shown in Figure 4 can also be described as the semiconductor device 100 shown in Figure 3, further comprising another semiconductor chip (11b) stacked on the surface of the semiconductor chip (11a).

[0100] Figure 5 is a schematic cross-sectional view showing another embodiment of the semiconductor device. The semiconductor device 120 shown in Figure 5 comprises a support member 12 and semiconductor chips 11a (first semiconductor chip), 11b (second semiconductor chip), 11c (third semiconductor chip), 11d (fourth semiconductor chip), 11e (fifth semiconductor chip), 11f (sixth semiconductor chip), 11g (seventh semiconductor chip), and 11h (eighth semiconductor chip) stacked on the support member 12. The four semiconductor chips 11a, 11b, 11c, and 11d are stacked at positions offset from each other in the lateral direction (a direction perpendicular to the stacking direction) for connection to connection terminals (not shown) formed on the surface of the support member 12. The four semiconductor chips 11e, 11f, 11g, and 11h stacked on top of them are stacked in a folded manner at positions offset from each other in the lateral direction (a direction perpendicular to the stacking direction) on the opposite side of the four semiconductor chips 11a, 11b, 11c, and 11d for connection to connection terminals (not shown) formed on the surface of the support member 12 (see Figure 5). The semiconductor chip 11a is bonded to the support member 12 by adhesive member 15a (cured product of adhesive composition (cured product of film-like adhesive)), and adjacent semiconductor chips are also bonded to each other by adhesive members 15b, 15c, 15d, 15e, 15f, 15g, and 15h (cured products of adhesive composition (cured product of film-like adhesive)). The connection terminals (not shown) of the semiconductor chips 11a, 11b, 11c, 11d, 11e, 11f, 11g, and 11h are electrically connected to external connection terminals via bonding wires 13, and the semiconductor chips 11a, 11b, 11c, 11d, 11e, 11f, 11g, and 11h are sealed by a sealing material 14. The semiconductor device 120 shown in Figure 5 can also be described as further comprising other semiconductor chips (11b, 11c, 11d, 11e, 11f, 11g, and 11h) stacked on the surface of the semiconductor chip (11a) in the semiconductor device 100 shown in Figure 3. The semiconductor device 120 shown in Figure 5 can also be described as having a folded structure in the stacked structure of the semiconductor chips.

[0101] Chip cracks that occur when connecting semiconductor chips with bonding wires are most likely to occur in semiconductor chips where there is no support (e.g., another semiconductor chip) below the connection terminal. For example, in the semiconductor device 120 shown in Figure 5, the semiconductor chip 11e (the fifth semiconductor chip) is stacked in a position shifted laterally (in a direction perpendicular to the stacking direction) relative to the semiconductor chip 11d (the fourth semiconductor chip) in a folded manner (see Figure 5), and there is no supporting semiconductor chip 11d (the fourth semiconductor chip) below the connection terminal of the semiconductor chip 11e (the connection point of the bonding wire 13, not shown). Therefore, in the semiconductor device 120 shown in Figure 5, chip cracks are most likely to occur when connecting the connection terminal of the semiconductor chip 11e (the fifth semiconductor chip) with the bonding wire 13. Since the cured film adhesive of this embodiment has a sufficient storage modulus, it is possible to suppress chip cracks caused by vibration during wire bonding, even in locations where chip cracks are likely to occur.

[0102] Although a semiconductor device has been described in detail above with respect to embodiments of the present disclosure, the present disclosure is not limited to the above embodiments. For example, Figure 5 illustrates a semiconductor device in which eight semiconductor chips are stacked, but the number of stacked semiconductor chips is not limited to this. Also, Figure 5 illustrates a semiconductor device in which semiconductor chips are stacked at positions offset from each other in the lateral direction (a direction perpendicular to the stacking direction), but a semiconductor device in which semiconductor chips are stacked at positions not offset from each other in the lateral direction (a direction perpendicular to the stacking direction) may also be used.

[0103] [Method for Manufacturing Semiconductor Devices] The semiconductor devices shown in Figures 3, 4, and 5 can be obtained by a method comprising the step of interposing the above-mentioned film-like adhesive between a semiconductor chip (first semiconductor chip) and a support member, or between a semiconductor chip (first semiconductor chip) and a semiconductor chip (second semiconductor chip), and bonding the semiconductor chip (first semiconductor chip) and the support member, or the semiconductor chip (first semiconductor chip) and a semiconductor chip (second semiconductor chip). More specifically, the above-mentioned film-like adhesive can be interposed between a semiconductor chip and a support member, or between a semiconductor chip (first semiconductor chip) and a semiconductor chip (second semiconductor chip), and these can be bonded together by heating and pressing, and then, if necessary, by going through a thermosetting step, a wire bonding step, a sealing step, a post-curing step, a heat melting step, etc.

[0104] As a method for interposing a film-like adhesive between a semiconductor chip (first semiconductor chip) and a support member, or between a semiconductor chip (first semiconductor chip) and a semiconductor chip (second semiconductor chip), as described later, a semiconductor chip with adhesive attached may be manufactured in advance and then attached to a support member or another semiconductor chip.

[0105] Next, an embodiment of a method for manufacturing a semiconductor device using the dicing-die bonding integrated film shown in Figure 2 will be described. Note that the method for manufacturing a semiconductor device using the dicing-die bonding integrated film is not limited to the method described below.

[0106] A semiconductor device can be obtained, for example, by a method comprising: a step of attaching a semiconductor wafer to the adhesive layer of the above-described dicing-die bonding integrated film (laminating step); a step of producing a plurality of individualized semiconductor chips with adhesive pieces by cutting the semiconductor wafer to which the adhesive layer has been attached (dicing step); and a step of bonding a first semiconductor chip with adhesive pieces, which has a first semiconductor chip and a first adhesive piece, to a support member via the first adhesive piece (first bonding step). The method for manufacturing a semiconductor device may further comprise a step of bonding a second semiconductor chip with adhesive pieces, which has a second semiconductor chip and a second adhesive piece, to the surface of the first semiconductor chip in the first semiconductor chip with adhesive pieces bonded to the support member via the second adhesive piece (second bonding step). The method for manufacturing a semiconductor device may further comprise a thermosetting step, a wire bonding step, a sealing step, a post-curing step, a heat melting step, and so on.

[0107] The lamination process involves pressing a semiconductor wafer onto the adhesive layer 1A of the dicing / die bonding integrated film 10, thereby bonding and holding it in place. This process may be carried out while applying pressure using a pressing means such as a pressure roll.

[0108] Examples of semiconductor wafers include single-crystal silicon, polycrystalline silicon, and compound semiconductors such as gallium arsenide.

[0109] The dicing process is the process of dicing a semiconductor wafer. This allows for the cutting of a semiconductor wafer into predetermined sizes, thereby manufacturing multiple individual semiconductor chips with adhesive pieces. Dicing can be performed, for example, from the circuit side of the semiconductor wafer according to conventional methods. In this process, various methods can be employed, such as a full-cut method in which an incision is made all the way to the dicing film, a method in which a half-incision is made in the semiconductor wafer and then the dicing film is stretched to divide it, or a method using a laser to divide it. The dicing apparatus used in this process is not particularly limited, and conventionally known apparatuses can be used.

[0110] A semiconductor chip is composed of, for example, a circuit layer and a semiconductor layer (for example, a compound semiconductor such as single-crystal silicon, polycrystalline silicon, or gallium arsenide). Examples of semiconductor chips include ICs (integrated circuits). Examples of support members include lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resin and epoxy resin; modified plastic films obtained by impregnating and curing a substrate such as glass nonwoven fabric with plastic such as polyimide resin or epoxy resin; and various ceramics such as alumina.

[0111] A method for manufacturing a semiconductor device may include a pickup step as needed. The pickup step is a step of picking up semiconductor chips with adhesive pieces attached in order to peel them off a dicing-die bonding integrated film. The method of pickup is not particularly limited, and various conventionally known methods can be used. For example, such a method may involve pushing up individual semiconductor chips with adhesive pieces attached from the dicing-die bonding integrated film side with a needle, and then picking up the pushed-up semiconductor chips with adhesive pieces attached using a pickup device.

[0112] In this case, if the adhesive layer is radiation-curable (e.g., ultraviolet light), the pickup can be performed after irradiating the adhesive layer with radiation. This reduces the adhesive strength of the adhesive layer to the adhesive chip, making it easier to remove the semiconductor chip with the adhesive chip attached. As a result, pickup becomes possible without damaging the semiconductor chip with the adhesive chip attached.

[0113] The first bonding step is to bond the semiconductor chip with a first adhesive piece formed by dicing to a support member for mounting the first semiconductor chip via the first adhesive piece. The semiconductor device manufacturing method may optionally include a step (second bonding step) of bonding a semiconductor chip with a second adhesive piece to the surface of the first semiconductor chip bonded to the support member via the second adhesive piece. Both bonding steps can be performed by pressure bonding. The pressure bonding conditions are not particularly limited and can be set as appropriate. For example, the pressure bonding conditions may be a temperature of 80 to 160°C, a pressure of 0.05 to 0.5 MPa, and a time of 0.5 to 5 seconds. The support member may be an example of a support member similar to the one described above.

[0114] The method for manufacturing a semiconductor device may optionally include a step of further thermal curing of adhesive pieces (the first adhesive piece in the semiconductor chip with the first adhesive piece, and the second adhesive piece in the semiconductor chip with the second adhesive piece) or a film-like adhesive (thermal curing step). By further thermal curing the semiconductor chip (first semiconductor chip) and the support member, and the adhesive pieces (the first adhesive piece in the semiconductor chip with the first adhesive piece, and the second adhesive piece in the semiconductor chip with the second adhesive piece) that bond the semiconductor chip (first semiconductor chip) and the semiconductor chip (second semiconductor chip), stronger adhesion and fixation becomes possible. When thermal curing is performed, pressure may be applied simultaneously to cure the adhesive. The heating temperature in this step can be appropriately changed depending on the components constituting the adhesive piece. The heating temperature may be, for example, 60 to 200°C, 80 to 190°C, or 100 to 180°C. Note that the temperature or pressure may be changed in stages. The heating time may be, for example, 1 to 120 minutes, 5 to 100 minutes, 10 to 80 minutes, or 15 to 60 minutes.

[0115] The method for manufacturing a semiconductor device may, if necessary, include a step of electrically connecting a first semiconductor chip and a second semiconductor chip to a support member with a bonding wire, or more specifically, a step of electrically connecting an electrode pad on the semiconductor chip to the tip of a terminal portion (inner lead) of the support member with a bonding wire (wire bonding step). Examples of bonding wires include gold wire, aluminum wire, copper wire, etc. The temperature when performing wire bonding may be in the range of 80 to 250°C or 80 to 220°C. The heating time may be several seconds to several minutes. Wire bonding may be performed by a combination of ultrasonic vibration energy and applied pressure to create a bond while heated within the above temperature range.

[0116] A method for manufacturing a semiconductor device may optionally include a step of sealing a semiconductor chip with a sealing material (sealing step). This step is performed to protect the semiconductor chip or bonding wire mounted on a support member. This step can be performed by molding a sealing resin (sealing resin) in a mold. The sealing resin may be, for example, an epoxy resin. The heat and pressure during sealing allow the sealing resin to fill in irregularities on the support member and voids at the adhesive interface, thereby preventing delamination due to air bubbles at the adhesive interface.

[0117] The method for manufacturing a semiconductor device may, if necessary, include a step (post-curing step) to completely cure the sealing resin that is not sufficiently cured in the sealing step. Even if the adhesive piece is not heat-cured in the sealing step, in this step, the adhesive piece can be heat-cured along with the curing of the sealing resin, enabling adhesive fixation. The heating temperature in this step can be appropriately set depending on the type of sealing resin, and may be in the range of 165 to 185°C, for example, and the heating time may be 0.5 to 8 hours.

[0118] A method for manufacturing a semiconductor device may, if necessary, include a step (heating and melting step) of heating a support member or a semiconductor chip bonded to a semiconductor chip using a reflow oven. In this step, the resin-encapsulated semiconductor device may be surface-mounted onto a mounting substrate such as a printed circuit board. Examples of surface mounting methods include reflow soldering, in which solder is supplied onto the printed circuit board in advance, then heated and melted with hot air or the like to perform soldering. Examples of heating methods include hot air reflow and infrared reflow. Furthermore, the heating method may involve heating the entire device or heating a localized area. The heating temperature may be, for example, in the range of 240 to 280°C.

[0119] The present disclosure will be described below in detail based on examples, but the present disclosure is not limited to these examples.

[0120] [Synthesis of (meth)acrylate polymers] <Production Example 1> Butyl acrylate (BA), ethyl acrylate (EA), glycidyl methacrylate (GMA), and acrylonitrile (AN) were prepared as monomers. The content of glycidyl methacrylate was adjusted to 8.8% by mass based on the total amount of monomers, and these monomers were polymerized using a solution polymerization method to obtain a solution containing the (meth)acrylate polymer of Production Example 1.

[0121] <Production Example 2> Using the same monomers as in Production Example 1, except that the glycidyl methacrylate content was adjusted to 11.0% by mass based on the total amount of monomers, a solution containing the (meth)acrylate polymer of Production Example 2 was obtained by adjusting the ratio of other monomers and / or polymerization conditions.

[0122] <Production Example 3> Using the same monomers as in Production Example 1, except that the glycidyl methacrylate content was adjusted to 13.4% by mass based on the total amount of monomers, and adjusting the ratio of other monomers and / or polymerization conditions, a solution containing the (meth)acrylate polymer of Production Example 3 was obtained.

[0123] <Production Example 4> Using the same monomers as in Production Example 1, except that the glycidyl methacrylate content was adjusted to 16.8% by mass based on the total amount of monomers, and adjusting the ratio of other monomers and / or polymerization conditions, a solution containing the (meth)acrylate polymer of Production Example 4 was obtained.

[0124] <Production Example 5> Using the same monomers as in Production Example 1, except that the glycidyl methacrylate content was adjusted to 22.2% by mass based on the total amount of monomers, and adjusting the ratio of other monomers and / or polymerization conditions, a solution containing the (meth)acrylate polymer of Production Example 5 was obtained.

[0125] <Production Example 6> Using the same monomers as in Production Example 1, except that the glycidyl methacrylate content was adjusted to 11.0% by mass based on the total amount of monomers, and adjusting the ratio of other monomers and / or polymerization conditions, a solution containing the (meth)acrylate polymer of Production Example 6 was obtained.

[0126] <Production Example 7> Using the same monomers as in Production Example 1, except that the glycidyl methacrylate content was adjusted to 22.2% by mass based on the total amount of monomers, and adjusting the ratio of other monomers and / or polymerization conditions, a solution containing the (meth)acrylate polymer of Production Example 7 was obtained.

[0127] [Evaluation of (meth)acrylate polymers] (Measurement of weight-average molecular weight (Mw)) As a sample for Mw measurement, a solution containing (meth)acrylate polymer was dissolved in tetrahydrofuran (THF) to prepare a 0.2 mass% THF solution. Mw was measured by gel permeation chromatography (GPC) and derived by conversion using a calibration curve for standard polystyrene. The GPC conditions are shown below. The results are shown in Table 1. Measuring device: SHOWDEX® GPC-101 (manufactured by RESONAC Corporation) Detector: Differential refractometer SHOWDEX RI-71S (manufactured by RESONAC Corporation) Column: SHOWDEX LF-804 + LF-804 (manufactured by RESONAC Corporation) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1 mL / min

[0128] (Measurement of epoxy value (epoxy index)) The epoxy value (epoxy index) was measured by an indicator titration method in accordance with JIS K7236:2009. The results are shown in Table 1.

[0129] (Calculation of P(A) / P(B)) For the (meth)acrylate polymer, an IR spectrum was obtained and P(A) / P(B) was calculated. First, for the (meth)acrylate polymer, a total reflection IR spectrum was obtained by the ATR method (total reflection measurement method). For the IR measurement, LUMOS II (manufactured by Bruker, ATR crystal: germanium, detector: MCT, infrared incident angle: 30°) was used. The IR measurement of the (meth)acrylate polymer was performed after background measurement, and atmospheric correction was performed on the obtained spectrum. Next, the spectrum was displayed with absorbance on the vertical axis and wavenumber (cm －１ ) on the horizontal axis. In the displayed spectrum, the wavenumbers of two points corresponding to the minimum absorbance values in the range of 880 cm －１ and 927 cm －１ were determined. The straight line connecting the two points at the said wavenumbers on the spectrum was taken as the baseline, and the area of the absorbance surrounded by the spectrum and the baseline was calculated as the area of the absorption peak (P(A)) derived from the antisymmetric stretching of the epoxy group. The straight line connecting the two points at 1661 cm －１ and 1842 cm －１ on the spectrum was taken as the baseline, and the area of the absorbance surrounded by the spectrum and the baseline was calculated as the area of the absorption peak (P(B)) derived from the stretching vibration of the carbonyl group. Based on the calculated P(A) and P(B), P(A) / P(B) was determined. The results are shown in Table 1.

[0130]

[0131] [Preparation of Film-like Adhesives] <Examples 1-10 and Comparative Example 1> (Preparation of Adhesive Varnish) The adhesive varnishes of Examples 1-10 and Comparative Example 1 were prepared by using each component shown in Tables 2 and 3 in the respective amounts (unit: parts by mass) shown in Tables 2 and 3. Specifically, cyclohexanone was added to a mixture of component (A) (components (A1) and (A2)) and stirred. Component (B) was added and stirred, and then components (D) and (E) were added and stirred until each component was homogeneous to obtain the adhesive varnishes of Examples 1-10 and Comparative Example 1. Note that each component shown in Tables 2 and 3 refers to the following, and the values ​​shown in Tables 2 and 3 refer to the parts by mass of the component (solid content) excluding solvents, etc.

[0132] (A) Component: Thermosetting resin component, (A1) Component: Epoxy resin (A1a-1) EXA-830CRP (Trade name, manufactured by DIC Corporation, Bisphenol F type epoxy resin, Epoxy equivalent: 155-163 g / eq, Softening point: Below 40°C, Liquid at 30°C) (A1b-1) N-500P-10 (Trade name, manufactured by DIC Corporation, o-Cresol novolac type epoxy resin, Epoxy equivalent: 204 g / eq, Softening point: 84°C, Solid at 30°C) (A1b-2) HP-4710 (Trade name, manufactured by DIC Corporation, Naphthalene type epoxy resin, Epoxy equivalent: 170 g / eq, Softening point: 95°C, Solid at 30°C)

[0133] • (A2) Ingredients: Phenolic resin (A2-1) PSM-4326 (product name, manufactured by Gun-ei Chemical Industry Co., Ltd., novolac-type phenolic resin, hydroxyl group equivalent: 105 g / eq, softening point: 120°C)

[0134] (B) Component: Elastomer, (B1) Component: (meth)acrylate polymer (B1-1) (meth)acrylate polymer from Production Example 1 (weight average molecular weight: 1,000,000, GMA content (based on total monomer amount): 8.8% by mass, epoxy value: 0.44 eq / kg, P(A) / P(B): 0.0076) (B1-2) (meth)acrylate polymer from Production Example 2 (weight average molecular weight: 850,000, GMA content (based on total monomer amount): 11.0% by mass, epoxy value: 0.55 eq / kg, P(A) / P(B): 0.0100) (B1-3) (meth)acrylate polymer from Production Example 3 (weight-average molecular weight: 750,000, GMA content (based on total monomer amount): 13.4% by mass, epoxy value: 0.67 eq / kg, P(A) / P(B): 0.0129) (B1-4) (meth)acrylate polymer from Production Example 4 (weight-average molecular weight: 650,000, GMA content (based on total monomer amount): 16.8% by mass, epoxy value: 0.84 eq / kg, P(A) / P(B): 0.0169) (B1-5) (meth)acrylate polymer from Production Example 5 (weight-average molecular weight: 600,000, GMA content (based on total monomer amount): 22.2% by mass, epoxy value: 1.11 eq / kg, P(A) / P(B): 0.0249) (B1-6) (meth)acrylate polymer from Production Example 6 (weight-average molecular weight: 800,000, GMA content (based on total monomer amount): 11.0% by mass, epoxy value: 0.66 eq / kg, P(A) / P(B): 0.0135) (B1-7) (meth)acrylate polymer from Production Example 7 (weight-average molecular weight: 650,000, GMA content (based on total monomer amount): 22.2% by mass, epoxy value: 1.66 eq / kg, P(A) / P(B): 0.0409) ・(B2) component: elastomer other than component (B1) (B2-1) SG-P3 (Trade name, manufactured by Nagase ChemteX Corporation, (meth)acrylate polymer of butyl acrylate (BA) / ethyl acrylate (EA) / glycidyl methacrylate (GMA) / acrylonitrile (AN), weight-average molecular weight: 800,000, GMA content (based on total monomer amount): 3.0% by mass, epoxy value: 0.15 eq / kg, P(A) / P(B): 0.0028)

[0135] (D) Ingredients: Coupling agent (D-1) Z-6119 (Trade name, manufactured by Dow Toray Corporation, γ-ureidopropyltriethoxysilane) (D-2) A-189 (Trade name, manufactured by Momentive Performance Materials Japan LLC, γ-mercaptopropyltrimethoxysilane)

[0136] (E) Ingredients: Curing accelerator (E-1) 2PZ-T (Trade name, manufactured by Shikoku Chemicals Co., Ltd., 2-phenylimidazole) (E-2) 2PZ-CN (Trade name, manufactured by Shikoku Chemicals Co., Ltd., 1-cyanoethyl-2-phenylimidazole)

[0137] (Preparation of film-like adhesives) The adhesive varnishes of Examples 1 to 10 and Comparative Example 1 were filtered through a 100-mesh filter and degassed under vacuum. A polyethylene terephthalate (PET) film with a release treatment and a thickness of 38 μm was prepared as a support film, and the adhesive varnish after degassing was applied onto the PET film. The applied adhesive varnish was heated and dried at 90°C for 5 minutes, followed by 140°C for 5 minutes to obtain the film-like adhesives of Examples 1 to 10 and Comparative Example 1 with a thickness of 5 μm in the B-stage state. In the film-like adhesives of Examples 1 to 10 and Comparative Example 1, the thickness of the film-like adhesive was adjusted by the amount of adhesive varnish applied.

[0138] [Evaluation of Film-like Adhesives] <Measurement of Storage Modulus> The storage modulus after curing was measured using the film-like adhesives of Examples 1 to 10 and Comparative Example 1. The storage modulus after curing was measured by the following method. Multiple layers of the film-like adhesive were laminated on a hot plate at 70°C using a rubber roll to obtain a laminate with a thickness of 160 μm. The obtained laminate was cut to a size of 6 mm or more in width and 35 mm or more in length, and after curing the laminate at 140°C for 30 minutes, it was cut to a size of 4 mm in width and 33 mm in length to prepare a sample for measurement. The sample was mounted on a dynamic viscoelasticity measuring device (Rheogel-E4000, manufactured by UBM Co., Ltd.), and the dynamic viscoelasticity of the sample was measured under the following conditions. From the measurement results, the storage modulus at 150°C was read and used as the storage modulus at 150°C for the film-like adhesive. The results are shown in Tables 2 and 3. The higher the storage modulus at 150°C (for example, 40 MPa or higher), the better it can compensate for the brittleness of semiconductor chips due to thinning. As a result, it tends to suppress the occurrence of chip cracks and improve wire bonding performance. (Conditions) ・Measurement mode: Tensile ・Chuck distance: 20 mm ・Heating rate: 10°C / min ・Frequency: 10 Hz ・Load: Automatic static load ・Measurement temperature: 30 to 270°C

[0139] <Measurement of Elongation at Break> The elongation at break at 25°C was measured for the film-like adhesives (5 μm thick) of Examples 1 to 10 and Comparative Example 1. More specifically, a sample for measurement was prepared by punching out a dumbbell-shaped No. 1 tensile test specimen from the film-like adhesive in the B-stage state and removing the support film. The sample was mounted on a high-speed tensile testing machine (RTF-1250-HS-PL, A&D Company, Limited) using a jig to ensure that the distance between the chucks was maintained, and measurements were taken under the following conditions. From the measurement results, the film length at the point of breakage was read, and the elongation at break of the film-like adhesive was calculated using formula (2). The results are shown in Tables 2 and 3. The larger the elongation at break at 25°C (for example, 300% or more), the better the processability when forming a thin film (for example, the ability to cut the film for circular die-cutting). Breaking elongation (%) = [(gauge length after test (mm) - gauge length (mm)) / gauge length (mm)] × 100 ... (2) (Conditions) Load cell: 50N Distance between chucks: 100mm Gauge length: 40mm Tensile speed: 100mm / min Measurement temperature: 25℃

[0140]

[0141]

[0142] As shown in Table 2, the film-like adhesives of Examples 1 to 4 exhibited excellent storage modulus and elongation at break, whereas the film-like adhesive of Comparative Example 1 did not have a sufficient storage modulus. Furthermore, as shown in Table 3, the film-like adhesives of Examples 5 to 10 exhibited excellent storage modulus and elongation at break. These results confirm that the film-like adhesive of this disclosure has good processability and excellent wire bonding properties.

[0143] 1...Film-type adhesive, 1A...Adhesive layer, 2...Base layer, 3...Adhesive layer, 4...Dicing film, 10...Dicing / die bonding integrated film, 11, 11a, 11b, 11c, 11d, 11e, 11f, 11g, 11h...Semiconductor chip, 12...Support member, 13...Bonding wire, 14...Sealing material, 15, 15a, 15b, 15c, 15d, 15e, 15f, 15g, 15h...Adhesive member, 16...Terminal, 100, 110, 120...Semiconductor device.

Claims

1. A film-like adhesive comprising a thermosetting resin component and an elastomer, wherein the elastomer comprises a (meth)acrylate polymer containing structural units derived from (meth)acrylate having epoxy groups, and the (meth)acrylate polymer satisfies at least one of the following conditions: (Condition A) The content of structural units derived from (meth)acrylate having epoxy groups is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer. (Condition B) The epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more. (Condition C) In the infrared absorption spectrum of the (meth)acrylate polymer, when P(A) is the area of ​​the absorption peak derived from the antisymmetric stretching of the epoxy group and P(B) is the area of ​​the absorption peak derived from the stretching vibration of the carbonyl group, P(A) and P(B) satisfy the following condition (1): P(A) / P(B) ≥ 0.0055 (1) 2. The film-like adhesive according to claim 1, which may further contain an inorganic filler, wherein the inorganic filler content is 0 to 5% by mass based on the total amount of the film-like adhesive.

3. The film-like adhesive according to claim 1, wherein the elastomer content is 30% by mass or more based on the total amount of the film-like adhesive.

4. The film-like adhesive according to claim 2, wherein the elastomer content is 30% by mass or more based on the total amount of the film-like adhesive.

5. A film-like adhesive according to any one of claims 1 to 4, wherein the thickness is 15 μm or less.

6. A dicing-die bonding integrated film comprising, in this order, a base layer, an adhesive layer, and an adhesive layer made of a film-like adhesive according to any one of claims 1 to 4.

7. A semiconductor device comprising: a semiconductor chip; a support member on which the semiconductor chip is mounted; and a cured film-like adhesive according to any one of claims 1 to 4, provided between the semiconductor chip and the support member to bond the semiconductor chip and the support member.

8. A method for manufacturing a semiconductor device, comprising: a step of attaching the adhesive layer of the dicing-die bonding integrated film described in claim 6 to a semiconductor wafer; a step of producing a plurality of individualized semiconductor chips with adhesive pieces by cutting the semiconductor wafer to which the adhesive layer has been attached; and a step of attaching a first semiconductor chip with adhesive pieces, which has a first semiconductor chip and a first adhesive piece, to a support member via the first adhesive piece.

9. A method for manufacturing a semiconductor device according to claim 8, further comprising: a step of thermally curing the first adhesive piece in the first adhesive piece-attached semiconductor chip at a temperature of 100 to 180°C for 15 to 60 minutes; and a step of electrically connecting the first semiconductor chip and the support member with a bonding wire.

10. The method for manufacturing a semiconductor device according to claim 8, further comprising the step of bonding a second semiconductor chip having a second semiconductor chip and a second adhesive piece, from among the plurality of individualized semiconductor chips with adhesive pieces, to the surface of the first semiconductor chip with adhesive piece bonded to the support member, via the second adhesive piece.

11. A method for manufacturing a semiconductor device according to claim 10, further comprising: a step of thermally curing the first adhesive piece in the first adhesive piece-attached semiconductor chip and the second adhesive piece in the second adhesive piece-attached semiconductor chip at a temperature of 100 to 180°C for 15 to 60 minutes; and a step of electrically connecting the first semiconductor chip and the second semiconductor chip and the support member with bonding wires.

12. A method for manufacturing a semiconductor device, comprising the step of interposing a film-like adhesive according to any one of claims 1 to 4 between a first semiconductor chip and a support member, or between a first semiconductor chip and a second semiconductor chip different from the first semiconductor chip, to bond the first semiconductor chip and the support member, or the first semiconductor chip and the second semiconductor chip.

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