(METH)acrylate polymer, film-shaped adhesive, dicing / die-bonding integrated film, and semiconductor device and production method therefor

Abstract

Disclosed is a (meth)acrylate polymer including a structural unit derived from a (meth)acrylate having an epoxy group. The (meth)acrylate polymer satisfies at least one of requirements A, B, and C.　Requirement A: The content of the structural unit derived from a (meth)acrylate having an epoxy group is 6 mass% or higher with respect to all the structural units of the (meth)acrylate polymer.　Requirement B: The (meth)acrylate polymer has an epoxy value of 0.40 eq / kg or greater.　Requirement C: The (meth)acrylate polymer gives an infrared absorption spectrum in which, when the area of an absorption peak derived from the antisymmetric stretching of an epoxy group is expressed by P(A) and the area of an absorption peak derived from the stretching vibration of a carbonyl group is expressed by P(B), then P(A) and P(B) satisfy the following expression (1).　(1): P(A) / P(B)≥0.0055

Description

(Meth)acrylate polymer, film adhesive, dicing / die bonding integrated film, semiconductor device and method for manufacturing the same.

[0001] This disclosure relates to (meth)acrylate polymers, film-like adhesives, dicing-die bonding integrated films, and semiconductor devices and methods 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 used as memory semiconductor packages for 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 in semiconductor packages.

[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 packages, semiconductor chips composed of a circuit layer and a semiconductor layer tend to have thicker circuit layers and thinner semiconductor layers. In such semiconductor packages, 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 (meth)acrylate polymer that, when applied to a film-like adhesive, can impart good processability and excellent wire bonding properties.

[0008] This disclosure provides (meth)acrylate polymers as described in [1] to [3], film-like adhesives as described in [4] to [7], a dicing-die bonding integrated film as described in [8], a semiconductor device as described in [9], and a method for manufacturing a semiconductor device as described in

[10] to

[14] . [1] A (meth)acrylate polymer comprising structural units derived from (meth)acrylate having epoxy groups, wherein the content of the 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. [2] A (meth)acrylate polymer comprising structural units derived from (meth)acrylate having epoxy groups, wherein the epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more. [3] A (meth)acrylate polymer comprising structural units derived from an epoxy group-containing (meth)acrylate, wherein, 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) [4] A film-like adhesive comprising a thermosetting resin component and an elastomer, wherein the elastomer comprises the (meth)acrylate polymer described in any of [1] to [3]. [5] The film-like adhesive according to [4], 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. [6] The film-like adhesive according to [4] or [5], wherein the elastomer content is 30% by mass or more based on the total amount of the film-like adhesive. [7] The film-like adhesive according to any one of [4] to [6], wherein the thickness is 15 μm or less. [8] A dicing-die bonding integrated film comprising, in this order, a base layer, an adhesive layer, and an adhesive layer made of the film-like adhesive according to any one of [4] to [7].[9] 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 [4] to [7] provided between the semiconductor chip and the support member to bond the semiconductor chip and the support member.

[10] A method for manufacturing a semiconductor device comprising: a step of attaching the adhesive layer of a dicing-die bonding integrated film according to [8] to a semiconductor wafer; a step of producing a plurality of individualized semiconductor chips with adhesive pieces by cutting the semiconductor wafer on which the adhesive layer is attached; and a step of bonding a first semiconductor chip having a first semiconductor chip and a first adhesive piece to a support member via the first adhesive piece.

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

[10] , further comprising: a step of thermally curing the first adhesive piece in the first semiconductor chip with adhesive piece 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.

[12] The method for manufacturing a semiconductor device according to

[10] , further comprising the step of bonding a second semiconductor chip having a second semiconductor chip and a second adhesive piece to the surface of the first semiconductor chip in the first semiconductor chip bonded to the support member via the second adhesive piece.

[13] The method for manufacturing a semiconductor device according to

[12] , further comprising the steps of thermal curing the first adhesive piece in the first semiconductor chip and the second adhesive piece in the second semiconductor chip with 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 bonding wires.

[14] A method for manufacturing a semiconductor device, comprising the step of interposing a film-like adhesive described in any of [4] to [7] 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 (meth)acrylate polymer that, when applied to a film-like adhesive, can impart good processability and excellent wire bonding properties. Furthermore, this disclosure provides a film-like adhesive using such a (meth)acrylate polymer. This disclosure also 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 this disclosure is not limited. 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] [(meth)acrylate polymer] The (meth)acrylate polymer of one embodiment includes structural units derived from (meth)acrylate having an epoxy group.

[0015] Examples of (meth)acrylates having an epoxy group include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, the (meth)acrylate having an epoxy group may be glycidyl (meth)acrylate or glycidyl methacrylate.

[0016] One embodiment of the (meth)acrylate polymer is embodiment A below. Another embodiment of the (meth)acrylate polymer is embodiment B below. Another embodiment of the (meth)acrylate polymer is embodiment C below. The (meth)acrylate polymer satisfies at least one of embodiments A, B, and C. Multiple combinations of embodiments A, B, and C are possible.

[0017] (Aspect 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.

[0018] The content of structural units derived from (meth)acrylate having epoxy groups can be calculated, for example, from the amount of monomer used in the production of (meth)acrylate polymers.

[0019] (Aspect B) The epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or higher. When the epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or higher, it is possible to impart good processability and excellent wire bonding properties when applied to a film-like adhesive. The epoxy value of the (meth)acrylate polymer is 0.42 eq / kg or higher, 0.50 eq / kg or higher, 0.55 eq / kg or higher, 0.60 eq / kg or higher, 0.65 eq / kg or higher, 0.70 eq / kg or higher, 0.75 eq / kg or higher, 0.80 eq / kg or higher, 0.85 eq / kg or higher, 0.90 eq / kg or higher, and 0.95 eq / kg, based on the total structural units of the (meth)acrylate polymer. It may be g 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.

[0020] In this specification, epoxy value (epoxy index) refers to the number of equivalent epoxy groups contained in 1 kg of (meth)acrylate polymer. The epoxy value (epoxy index) is a value measured by indicator titration in accordance with JIS K7236:2009.

[0021] (Aspect C) In the infrared absorption spectrum of a (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)

[0022] The P(A) / P(B) ratio is 0.0055 or higher. When P(A) / P(B) is 0.0055 or higher, it is possible to provide good processability and excellent wire bonding properties when applied to a film-type adhesive. P(A) / P(B) may be 0.0060 or greater, 0.0070 or greater, 0.0080 or greater, 0.0090 or greater, 0.0100 or greater, 0.0120 or greater, 0.0140 or greater, 0.0160 or greater, 0.0180 or greater, 0.0200 or greater, or 0.0220 or greater, and may be 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.

[0023] The epoxy group mainly originates from (meth)acrylate having the epoxy group as its structural unit, and the carbonyl group mainly originates from (meth)acrylate having the epoxy group as its structural unit. That is, P(A) / P(B) represents the ratio of (meth)acrylate having the epoxy group to the total amount of (meth)acrylate in the (meth)acrylate polymer. The area of ​​the absorption peak (P(A)) due to the antisymmetric stretching of the epoxy group and the area of ​​the absorption peak (P(B)) due to the stretching vibration of the carbonyl group can be calculated, for example, by the following method.

[0024] First, the total internal reflection (IR) spectrum of the (meth)acrylate polymer is obtained using the ATR method (total internal reflection measurement). For IR measurement, for example, a LUMOS II (Bruker, ATR crystal: germanium, detector: MCT, infrared incidence angle: 30°) can be used. The IR measurement for the (meth)acrylate polymer is performed after background measurement, and the obtained spectrum is corrected for atmospheric pressure. Next, the vertical axis is set to absorbance and the horizontal axis to wavenumber (cm²). －１ The spectrum is displayed, and in the displayed spectrum, 885 cm⁻¹ －１ and 925 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.

[0025] The epoxy value in Embodiment B and the P(A) / P(B) in Embodiment C can also be determined by extracting the (meth)acrylate polymer from the film-like adhesive described later and obtaining the extracted (meth)acrylate polymer. Examples of methods for extracting the (meth)acrylate polymer from the film-like adhesive include 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 its 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.

[0026] 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.

[0027] Other (meth)acrylates 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, and 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 acrylate; alkenyl (meth)acrylates having alkenyl groups with 2 to 18 carbon atoms, such as 3-butenyl (meth)acrylate; and aromatic rings, such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate. (meth)acrylates; methoxytetraethylene glycol (meth)acrylate, methoxyhexaethylene glycol (meth)acrylate, methoxyoctaethylene glycol (meth)acrylate, methoxynonaethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxyheptapropylene glycol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, and other alkoxy polyalkylene glycol (meth)acrylates; alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; hydroxyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 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, tripropylene glycol mono(meth)acrylate, and octapropylene 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.

[0028] 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 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.

[0029] 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 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] (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. In addition, types of polymerization reactions include radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, living cationic polymerization, living anionic polymerization, coordination polymerization, immortal polymerization, as well as ATRP (atomic transfer radical polymerization) and RAFT (reversible addition-cleavage chain transfer 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.

[0034] Here, we will describe a method for producing (meth)acrylate polymers by radical polymerization using solution polymerization.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] The reaction temperature can be appropriately set according to the type of radical polymerization initiator used and the like. The reaction temperature may be, for example, 40 to 125 °C or 60 to 120 °C. The reaction time can also be appropriately set according to the type of radical polymerization initiator used and the like. The reaction time may be, for example, 1 to 24 hours or 3 to 15 hours.

[0040] [Film Adhesive] FIG. 1 is a schematic cross-sectional view showing an embodiment of a film adhesive. The film adhesive 1 shown in FIG. 1 may be thermosetting and may be able to reach a fully cured (C-stage) state after curing treatment through a semi-cured (B-stage) state. The film 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 adhesive 1 contains a (meth)acrylate polymer that can impart excellent wire bonding properties as an elastomer, it can be suitably used for bonding semiconductor chips to each other.

[0041] The film adhesive 1 may contain a thermosetting resin component (hereinafter sometimes referred to as the “(A) component”) and an elastomer (hereinafter sometimes referred to as the “(B) component”). The (B) component includes the above-mentioned (meth)acrylate polymer (hereinafter sometimes referred to as the “(B1) component”). The (A) component may include, for example, an epoxy resin (hereinafter sometimes referred to as the “(A1) component”) and a phenol resin (hereinafter sometimes referred to as the “(A2) component”). In addition to the (A) component and the (B) component, the film adhesive 1 may further contain an inorganic filler (hereinafter sometimes referred to as the “(C) component”), a coupling agent (hereinafter sometimes referred to as the “(D) component”), a curing accelerator (hereinafter sometimes referred to as the “(E) component”), and other components.

[0042] (A) component: thermosetting resin component・(A1) component: epoxy resin The (A1) component can be used without particular limitation as long as it has an epoxy group in the molecule. As the (A1) component, for example, 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; polyfunctional phenols, diglycidyl ether compounds of polycyclic aromatics such as anthracene, etc. can be mentioned. Among these, the (A1) component may contain a cresol novolac type epoxy resin, a bisphenol F type epoxy resin, or a bisphenol A type epoxy resin from the viewpoints of the tackiness, flexibility, etc. of the film. The bisphenol F type epoxy resin, for example, has a relatively low softening point, and many have a softening point of 40 °C or lower.

[0043] The (A1) component may contain a liquid epoxy resin having a softening point of 40 °C or lower (or a liquid epoxy resin that is liquid at 30 °C, hereinafter sometimes referred to as the "(A1a) component"). The (A1) component may be a combination of the (A1a) component and a solid epoxy resin having a softening point exceeding 40 °C (or a solid epoxy resin that is solid at 30 °C, hereinafter sometimes referred to as the "(A1b) component"). When the (A1) component contains the (A1a) component, there is a tendency to more easily improve the storage elastic modulus after curing. Also, when the (A1) component is a combination of the (A1a) component and the (A1b) component, there is a tendency to more easily achieve further thinning of the film.

[0044] In this specification, the softening point means a value measured by the ring and ball method in accordance with JIS K7234:1986.

[0045] 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).

[0046] 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.

[0047] 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.

[0048] The epoxy equivalent of component (A1) is not particularly limited, but may be 90 to 300 g / eq or 110 to 290 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.

[0049] • 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 highly crosslinked, improving the storage modulus after curing.

[0050] (A2) Component (A2) can be used without particular limitation as long as it has a phenolic hydroxyl group in its molecule. Component (A2) is not particularly limited 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, the phenolic resin may include novolac-type phenolic resin or phenylaralkyl-type phenolic resin.

[0051] The hydroxyl group equivalent of component (A2) may be 70 g / eq or more, or 70 to 300 g / eq. When the hydroxyl group equivalent of component (A2) is 70 g / eq or more, the storage modulus tends to improve further, and when it is 300 g / eq or less, it is possible to prevent problems caused by foaming, outgassing, etc.

[0052] (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.

[0053] (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: 99-106°C).

[0054] The ratio of the epoxy equivalent of component (A1) to the hydroxyl group equivalent of component (A2) (epoxy equivalent of component (A1) / hydroxyl group equivalent of 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] (B) Component: Elastomer. 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.

[0059] 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 acrylic resins other than component (B1), polyester resins, polyamide resins, polyimide resins, silicone resins, butadiene resins; and modified versions of these resins. Examples of component (B2) include polymers having organopolysiloxanes as side chains.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] (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).

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] (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.

[0070] (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.

[0071] Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole.

[0072] Component (E) may contain 2-phenylimidazole because it readily promotes hardening at low temperatures.

[0073] The film-like adhesive may further contain other components. Examples of other components include pigments, ion capture agents, antioxidants, and so on.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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

[0078] The elongation at break of the film-like adhesive 1 at 25°C may be 150% or more, and may be 180% or more, 200% or more, 220% or more, 240% or more, 260% or more, 280% or more, 300% or more, or 320% or more. When the elongation at break is 150% 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 upper limit to the elongation at break, but it may be, for example, 1000% or less, 800% or less, 600% or less, or 500% or less.

[0079] 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 was prepared by punching out a dumbbell-shaped No. 1 tensile test specimen from a film-like adhesive (5 mm thick) in the B-stage state and removing the support film. The sample was mounted on a high-speed tensile testing machine (e.g., RTF-1250-HS-PL, A&D Co., Ltd.) using a jig to ensure that the distance between the chucks was maintained, and the measurement was performed under the following conditions. From the measurement results, the film length at the point where the film broke was read, and the elongation at break of the film-like adhesive was calculated using formula (1). Elongation at break (%) = (distance between gauge marks after test (mm) - distance between gauge marks (mm)) / distance between gauge marks (mm) ... (1) (Conditions) Load cell: 50 N Distance between chucks: 40 mm Distance between gauge marks: 20 mm Tensile speed: 100 mm / min Measurement temperature: 25°C

[0080] 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.

[0081] 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.

[0082] Mixing or kneading can be carried out using conventional agitators, dispersers, three-roll mills, ball mills, and other dispersers, in appropriate combinations.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] [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.

[0087] The dicing film 4 comprises a base layer 2 and an adhesive layer 3 provided on the base layer 2.

[0088] 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.

[0089] 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 semiconductor chips from scattering during the dicing process and low enough adhesive strength to avoid damaging the semiconductor chips 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 non-radiation-curable. The radiation may be, for example, ultraviolet light. A non-radiation-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).

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] Film-type adhesives can also be used, for example, as protective sheets to protect the back surface of semiconductor chips in flip-chip semiconductor devices, or as sealing sheets to seal the space between the surface of semiconductor chips in flip-chip semiconductor devices and the adherend.

[0096] 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.

[0097] [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.

[0098] 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).

[0099] 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, and 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 an adhesive member 15a (cured product of the adhesive composition (cured product of the film-like adhesive)), and adhesive members 15b, 15c, 15d, 15e, 15f, 15g, and 15h (cured product of the adhesive composition (cured product of the film-like adhesive)) are interposed between the seven semiconductor chips 11b, 11c, 11d, 11e, 11f, 11g, and 11h, respectively. 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, 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.

[0100] 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.

[0101] Although the embodiments of the present disclosure have been described in detail above, 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 the 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 the semiconductor chips are stacked at positions not offset from each other in the lateral direction (a direction perpendicular to the stacking direction) is also possible.

[0102] [Method for Manufacturing Semiconductor Devices] The semiconductor devices (semiconductor packages) 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.

[0103] 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.

[0104] 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.

[0105] 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 the 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 (a step of bonding the semiconductor chip with adhesive pieces to the support member via the adhesive piece) (a first bonding step). The method for manufacturing a semiconductor device may further comprise a step of bonding the 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 on the first semiconductor chip with adhesive pieces bonded to the support member via the second adhesive piece (a step of bonding another semiconductor chip with adhesive pieces to the surface of a semiconductor chip bonded to a support member via the adhesive piece of the other semiconductor chip with adhesive pieces) (a second bonding step). The method for manufacturing a semiconductor device may further include a thermosetting step, a wire bonding step, a sealing step, a post-curing step, a heating and melting step, and so on.

[0106] 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.

[0107] Examples of semiconductor wafers include single-crystal silicon, polycrystalline silicon, various ceramics, and compound semiconductors such as gallium arsenide.

[0108] The dicing process is the process of dicing a semiconductor wafer. This allows for the cutting of a semiconductor wafer into predetermined sizes, enabling the production of 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 the wafer is divided by cooling and pulling, or a method using a laser to divide the wafer. The dicing apparatus used in this process is not particularly limited, and conventionally known apparatuses can be used.

[0109] A semiconductor chip is composed of, for example, a circuit layer and a semiconductor layer (for example, single-crystal silicon, polycrystalline silicon, various ceramics, compound semiconductors such as 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 plastics such as polyimide resin and epoxy resin; and ceramics such as alumina.

[0110] 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.

[0111] 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.

[0112] 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 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 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 load of 5 to 15 N, and a time of 1 to 10 seconds. The support member may be an example of a support member similar to the one described above.

[0113] 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 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 (the first semiconductor chip) and the support member, stronger adhesion and fixation become 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 of the adhesive piece. The heating temperature may be, for example, 60 to 200°C, 80 to 190°C, or 100 to 180°C. 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.

[0114] 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, 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.

[0115] 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 embed the support member and residue, preventing delamination due to air bubbles at the adhesive interface.

[0116] 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 about 0.5 to 8 hours.

[0117] A method for manufacturing a semiconductor device may optionally 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, a resin-encapsulated semiconductor device may be surface-mounted onto the support member. Examples of surface mounting methods include reflow soldering, in which solder is supplied onto a 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. 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.

[0118] The present disclosure will be described below in detail based on examples, but the present disclosure is not limited to these examples.

[0119] [Synthesis of (meth)acrylate polymers] <Example 1-1> 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 Example 1-1.

[0120] <Example 1-2> A solution containing the (meth)acrylate polymer of Example 1-2 was obtained in the same manner as in Example 1-1, except that the glycidyl methacrylate content was adjusted to 11.0% by mass based on the total amount of monomers.

[0121] <Example 1-3> A solution containing the (meth)acrylate polymer of Example 1-3 was obtained in the same manner as in Example 1-1, except that the glycidyl methacrylate content was adjusted to 13.4% by mass based on the total amount of monomers.

[0122] <Example 1-4> A solution containing the (meth)acrylate polymer of Example 1-4 was obtained in the same manner as in Example 1-1, except that the glycidyl methacrylate content was adjusted to 16.8% by mass based on the total amount of monomers.

[0123] <Example 1-5> A solution containing the (meth)acrylate polymer of Example 1-5 was obtained in the same manner as in Example 1-1, except that the glycidyl methacrylate content was adjusted to 22.2% by mass based on the total amount of monomers.

[0124] [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

[0125] (Measurement of epoxy value (epoxy index)) The epoxy value (epoxy index) was measured by indicator titration in accordance with JIS K7236:2009. The results are shown in Table 1.

[0126] (Calculation of P(A) / P(B)) For the (meth)acrylate polymer, IR spectra were obtained and P(A) / P(B) was calculated. First, for the (meth)acrylate polymer, total internal reflection IR spectra were obtained using the ATR method (total internal reflection measurement method). For IR measurements, a LUMOS II (Bruker, ATR crystal: germanium, detector: MCT, infrared incidence angle: 30°) was used. The IR measurement for the (meth)acrylate polymer was performed after background measurement, and the obtained spectra were corrected for atmospheric conditions. Next, the vertical axis was plotted as absorbance and the horizontal axis as wavenumber (cm²). －１ The spectrum is displayed, and in the displayed spectrum, 885 cm⁻¹ －１ and 925 cm －１The wavenumbers of two points corresponding to the minimum value of absorbance within the range were determined, and the straight line connecting the two points of the wavenumbers on the spectrum was used as the baseline. The area of absorbance enclosed 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. 1661 cm on the spectrum －１ and 1842 cm －１ The straight line connecting the two points was used as the baseline, and the area of absorbance enclosed 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.

[0127]

[0128] [Preparation of Film状 Adhesive] <Examples 2-1 to 2-7 and Comparative Example 2-1> (Preparation of Adhesive Varnish) By using each component shown in Tables 2 and 3 at each content (unit: part by mass) shown in Tables 2 and 3, the adhesive varnishes of Examples 2-1 to 2-7 and Comparative Example 2-1 were prepared. Specifically, cyclohexanone was added to the mixture composed of component (A) (components (A1) and (A2)), and they were stirred and mixed. Component (B) was added thereto and stirred, and further components (D) and (E) were added, and they were stirred until each component became uniform to obtain the adhesive varnishes of Examples 2-1 to 2-7 and Comparative Example 2-1. Each component shown in Tables 2 and 3 means the following, and the numerical values shown in Tables 2 and 3 mean the parts by mass of the components (solid content) excluding solvents and the like.

[0129] Component (A): Thermosetting resin component - Component (A1): Epoxy resin (A1a-1) EXA830-CRP (trade name, manufactured by DIC Corporation, bisphenol F type epoxy resin, epoxy equivalent: 155 to 163 g / eq, softening point: 40 °C or lower, liquid at 30 °C) (A1b-1) N-500P-10 (trade name, manufactured by DIC Corporation, o-cresol novolak type epoxy resin, epoxy equivalent: 204 g / eq, softening point: 75 to 85 °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)

[0130] • (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)

[0131] (B) Component: Elastomer, (B1) Component: (meth)acrylate polymer (B1-1) (meth)acrylate polymer from Example 1-1 (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 Example 1-2 (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 Example 1-3 (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 Example 1-4 (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 Example 1-5 (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) • (B2) component: Elastomer other than component (B1) (B2-1) SG-P3 (product 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)

[0132] (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)

[0133] (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)

[0134] (Preparation of film-like adhesives) The adhesive varnishes of Examples 2-1 to 2-7 and Comparative Example 2-1 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 2-1 to 2-7 and Comparative Example 2-1 with a thickness of 5 μm in the B-stage state. In the film-like adhesives of Examples 2-1 to 2-7 and Comparative Example 2-1, the thickness of the film-like adhesive was adjusted by the amount of adhesive varnish applied.

[0135] [Evaluation of Film-like Adhesives] <Measurement of Storage Modulus> The storage modulus after curing was measured using the film-like adhesives of Examples 2-1 to 2-7 and Comparative Example 2-1. The storage modulus after curing was measured by the following method. Multiple layers of film-like adhesive were laminated on a 70°C hot plate 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 of the film-like adhesive at 150°C. 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

[0136] <Measurement of Elongation at Break> The elongation at break at 25°C was measured for the film-like adhesives (5 mm thick) of Examples 2-1 to 2-7 and Comparative Example 2-1. 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 (1). The results are shown in Tables 2 and 3. The larger the elongation at break at 25°C (for example, 150% or more), the better the processability when forming a thin film (for example, the ability to cut the film for circular die-cutting). Elongation at break (%) = (Gauge length after test (mm) - Gauge length (mm)) / Gauge length (mm) ... (1) (Conditions) Load cell: 50N Distance between chucks: 40mm Gauge length: 20mm Tensile speed: 100mm / min Measurement temperature: 25℃

[0137]

[0138]

[0139] As shown in Table 2, the film adhesives of Examples 2-1 to 2-3 exhibited excellent storage modulus and elongation at break, whereas the film adhesive of Comparative Example 2-1 did not have a sufficient storage modulus. Furthermore, as shown in Table 3, the film adhesives of Examples 2-4 to 2-7 exhibited excellent storage modulus and elongation at break. These results confirm that the (meth)acrylate polymer of this disclosure, when applied to a film adhesive, can impart good processability and excellent wire bonding properties.

[0140] 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 (meth)acrylate polymer containing structural units derived from (meth)acrylate having an epoxy group, wherein the content of the structural units derived from (meth)acrylate having an epoxy group is 6% by mass or more, based on the total structural units of the (meth)acrylate polymer.

2. A (meth)acrylate polymer comprising structural units derived from (meth)acrylate having epoxy groups, wherein the epoxy value of the (meth)acrylate polymer is 0.40 eq / kg or more.

3. A (meth)acrylate polymer comprising structural units derived from (meth)acrylate having an epoxy group, wherein, 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) 4. A film-like adhesive comprising a thermosetting resin component and an elastomer, wherein the elastomer comprises a (meth)acrylate polymer according to any one of claims 1 to 3.

5. The film-like adhesive according to claim 4, 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.

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

7. The film-like adhesive according to claim 5, wherein the elastomer content is 30% by mass or more based on the total amount of the film-like adhesive.

8. The film-like adhesive according to claim 4, wherein the thickness is 15 μm or less.

9. A dicing-die bonding integrated film comprising, in this order, a base layer, an adhesive layer, and an adhesive layer made of the film-like adhesive described in claim 4.

10. A semiconductor device comprising: a semiconductor chip; a support member on which the semiconductor chip is mounted; and a cured product of the film-like adhesive according to claim 4, provided between the semiconductor chip and the support member to bond the semiconductor chip and the support member.

11. A method for manufacturing a semiconductor device, comprising: a step of attaching the adhesive layer of a dicing-die bonding integrated film according to claim 9 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 the 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.

12. A method for manufacturing a semiconductor device according to claim 11, 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.

13. The method for manufacturing a semiconductor device according to claim 11, further comprising the step of bonding a second semiconductor chip having a second semiconductor chip and a second adhesive piece to the surface of the first semiconductor chip in the first semiconductor chip bonded to the support member via the second adhesive piece.

14. A method for manufacturing a semiconductor device according to claim 13, 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.

15. A method for manufacturing a semiconductor device, comprising the step of interposing the film-like adhesive described in claim 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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