Film adhesive, dicing die-bonding film, semiconductor device, and production method for same

Abstract

Provided is a film adhesive that contains a thermosetting resin component and an elastomer and may also contain an inorganic filler. The inorganic filler content is 0–5 mass% of the total mass of the film adhesive. The shear viscosity at 120°C is no more than 10000 Pa⋅s.

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 layers of semiconductor elements (semiconductor chips), have become widespread and are being used as semiconductor devices (semiconductor packages) for 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. Consequently, semiconductor wafers are becoming thinner, which can lead to problems such as wafer cracking during processing and a decrease in yield. Therefore, as semiconductor wafers become thinner (for example, 50 μm or less), there is a shift from conventional physical grinding methods to new processing methods.

[0003] One new processing method that has been proposed in recent years involves irradiating the inside of a semiconductor wafer along the cutting line with laser light to form a modified region, and then cutting the semiconductor wafer by expanding the outer edge (for example, Patent Documents 1 and 2). This method is called stealth dicing. With the development of new processing methods such as stealth dicing, the development of functional films that can be used with these methods is progressing. As such functional films, for example, a dicing-die bonding integrated film that combines the performance of a dicing film and a die bonding film has been reported (for example, Patent Documents 3 and 4).

[0004] Japanese Patent Publication No. 2002-192370, Japanese Patent Publication No. 2003-338467, Japanese Patent Publication No. 2015-211080, Japanese Patent Publication No. 2016-115775

[0005] Incidentally, in the manufacturing process of semiconductor devices, when modified regions are formed and separated by stealth dicing, expansion under cooling conditions (hereinafter sometimes referred to as "cooled expansion") is sometimes performed. However, when a conventional dicing-die bonding integrated film is applied to cooled expansion, undivided portions may occur in the adhesive layer, which consists of a film-like adhesive (die bonding film). This tendency for undivided portions to occur becomes more pronounced as the thickness of the film-like adhesive decreases (for example, 15 μm or less). When undivided portions of the adhesive layer occur, it leads to problems such as a decrease in yield and a decrease in production time efficiency due to the need to sort out undivided products.

[0006] Therefore, the main objective of this disclosure is to provide a film-like adhesive that exhibits excellent cooling and discontinuity.

[0007] The present inventors conducted diligent studies to solve the above problems and discovered that film-like adhesives with an extremely low inorganic filler content tend to exhibit excellent cooling-disruption properties when the shear viscosity at 120°C is within a predetermined range, thus completing the present invention.

[0008] This disclosure provides the film-like adhesives described in [1] to [7], the dicing-die bonding integrated film described in [8], the semiconductor device described in [9] and

[10] , and the method for manufacturing the semiconductor device described in

[12] and

[13] . [1] A film-like adhesive containing a thermosetting resin component and an elastomer, and possibly further containing 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, and the shear viscosity at 120°C is 10,000 Pa·s or less. [2] The film-like adhesive according to [1], wherein the content of the thermosetting resin component is 40% by mass or more based on the total amount of the film-like adhesive. [3] The film-like adhesive according to [1] or [2], wherein the thermosetting resin component contains an epoxy resin and a phenolic resin. [4] The film-like adhesive according to any one of [1] to [3], wherein the content of the elastomer 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 [1] to [4], wherein the storage modulus of the cured product at 150°C is 20 MPa or more when the film-like adhesive is cured at 140°C for 30 minutes. [6] A film-like adhesive according to any one of [1] to [5], wherein the thickness is 15 μm or less. [7] A film-like adhesive according to any one of [1] to [6], used in a manufacturing process for a semiconductor device comprising a plurality of semiconductor chips stacked on top of each other. [8] A dicing-die bonding integrated film comprising a base layer, an adhesive layer, and an adhesive layer made of the film-like adhesive according to any one of [1] to [6], in this order. [9] A semiconductor device comprising: a first semiconductor chip; a support member on which the first semiconductor chip is mounted; and a cured product of the film-like adhesive according to any one of [1] to [6], provided between the first semiconductor chip and the support member to bond the first semiconductor chip and the support member.

[10] The semiconductor device according to [9], further comprising a second semiconductor chip different from the first semiconductor chip, which is stacked on the surface of the first semiconductor chip.A method for manufacturing a semiconductor device, comprising: a step of attaching the adhesive layer of the dicing-die bonding integrated film described in

[11] and [8] to a semiconductor wafer; a step of dicing the semiconductor wafer to which the adhesive layer has been attached; a step of producing a plurality of individualized semiconductor chips with adhesive pieces by expanding the base layer under cooling conditions; a step of picking up a first semiconductor chip having a first semiconductor chip and a first adhesive piece from the plurality of individualized semiconductor chips with adhesive pieces from the adhesive layer; and a step of bonding the first semiconductor chip with adhesive pieces to a support member via the first adhesive piece.

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

[11] , wherein the step of producing the semiconductor chip with adhesive pieces includes a step of expanding the base layer under cooling conditions and a step of heating the adhesive layer on the outer periphery of the semiconductor chip with adhesive pieces to shrink the adhesive layer and the base layer on the inner side of the outer periphery.

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

[11] or

[12] , 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.

[0009] This disclosure provides a film-like adhesive with excellent cooling and discontinuity. Some forms of film-like adhesives also tend to have excellent storage modulus after curing. Furthermore, this disclosure provides a dicing-die bonding integrated film and a semiconductor device using such a film-like adhesive. Moreover, 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 a 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.

[0015] The film-like adhesive 1 may contain a thermosetting resin component (hereinafter sometimes referred to as "component (A)") and an elastomer (hereinafter sometimes referred to as "component (B)"), and may further contain an inorganic filler (hereinafter sometimes referred to as "component (C)"). The film-like adhesive 1 does not have to contain component (C). Component (A) may, for example, contain an epoxy resin (hereinafter sometimes referred to as "component (A1)") and a phenolic resin (hereinafter sometimes referred to as "component (A2)"). In addition to components (A), (B), and (C), the film-like adhesive 1 may further contain a coupling agent (hereinafter sometimes referred to as "component (D)"), a curing accelerator (hereinafter sometimes referred to as "component (E)"), and other components.

[0016] The shear viscosity of the film-like adhesive 1 at 120°C is 10,000 Pa·s or less, and may be 9,000 Pa·s or less, 8,000 Pa·s or less, 7,500 Pa·s or less, 7,000 Pa·s or less, 6,500 Pa·s or less, 6,000 Pa·s or less, 5,500 Pa·s or less, 5,000 Pa·s or less, or 4,500 Pa·s or less. When the shear viscosity is 10,000 Pa·s or less, it tends to have excellent cooling discontinuity. The shear viscosity of the film-like adhesive 1 at 120°C may be, for example, 500 Pa·s or more, 1,000 Pa·s or more, 1,500 Pa·s or more, or 2,000 Pa·s or more.

[0017] In this specification, the shear viscosity of a film-type adhesive at 120°C can be measured, for example, by the following method. Multiple layers of the film-type adhesive are stacked on a 70°C hot plate using a rubber roll to obtain a laminate with a thickness of 300 to 400 μm. The obtained laminate is cut to a size of φ9 mm to prepare a sample for measurement. The sample is mounted on a measuring jig of a rotary viscoelasticity measuring device (e.g., ARES-G2, manufactured by T.A. Instrument Japan Co., Ltd.), and the viscoelasticity of the sample is measured under the following conditions. From the measurement results, the viscosity (complex viscosity ratio) at 120°C is read and taken as the shear viscosity of the film-type adhesive at 120°C. (Conditions) ・Measuring jig: Parallel plate, aluminum, φ8 mm ・Frequency: 1 Hz ・Heating rate: 5°C / min ・Strain: 5% ・Measurement temperature: 35 to 180°C

[0018] For example, the shear viscosity at 120°C can be reduced by employing the following methods: • Increase the content of component (A) in the film adhesive. • Increase the content of component (B) in the film adhesive. • Decrease the content of component (C) in the film adhesive. • Decrease the content of component (E) in the film adhesive.

[0019] The following describes each component constituting the film-like adhesive of this embodiment. By employing the components shown below, it tends to be easier to produce a film-like adhesive that satisfies the above-mentioned shear viscosity condition at 120°C.

[0020] (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.

[0021] 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.

[0022] 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.

[0023] 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).

[0024] 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).

[0025] When component (A1) is a combination of component (A1a) and component (A1b), the content of component (A1a) may be 1% by mass or more, 3% by mass or more, 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.

[0026] 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 99% by mass or less, 97% by mass or less, 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.

[0027] 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.

[0028] • 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.

[0029] 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.

[0030] 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.

[0031] (A2) The softening point of component (A2) is not particularly limited, but may be, for example, 70°C or higher, 80°C or higher, 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.

[0032] (A2) Examples of commercially available components include MEH-7800M (trade name, manufactured by Meiwa Kasei Co., Ltd. (now UBE Co., Ltd.), phenylaralkyl type phenolic resin, hydroxyl group equivalent: 174 g / eq, softening point: 82°C), 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).

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] (B) Component: Elastomer Component (B) is an elastomer (a resin having rubber-like elasticity). Examples of component (B) include (meth)acrylic resin (including (meth)acrylic rubber), urethane resin (including urethane rubber), silicone resin (including silicone rubber), styrene-based elastomer, etc. Among these, component (B) may be a (meth)acrylic resin ((meth)acrylic rubber) having constituent units derived from (meth)acrylic acid ester as its main component, because it has excellent cooling and discontinuity, fewer ionic impurities and superior heat resistance, makes it easier to ensure connection reliability of semiconductor devices, and also has excellent fluidity. The content of constituent units derived from (meth)acrylic acid ester in component (B) may be, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more, based on the total amount of constituent units. The (meth)acrylic resin may contain constituent units derived from (meth)acrylic acid ester having crosslinkable functional groups such as epoxy groups, alcoholic or phenolic hydroxyl groups, or carboxyl groups.

[0038] The glass transition temperature (Tg) of component (B) may be 5°C or higher, and may also be 10°C or higher. When the Tg of component (B) is 5°C or higher, it is possible to further improve the adhesive strength of the adhesive composition, and furthermore, it tends to prevent the flexibility of the film-like adhesive from becoming too high. There is no particular upper limit to the Tg of component (B), but it may be, for example, 55°C or lower, 50°C or lower, 45°C or lower, 40°C or lower, 35°C or lower, 30°C or lower, or 25°C or lower. When the Tg of component (B) is 55°C or lower, it tends to suppress the decrease in flexibility of the film-like adhesive. This tends to make it easier to adequately fill voids when attaching the film-like adhesive to a semiconductor wafer. Here, the glass transition temperature (Tg) refers to the value measured using a DSC (Differential Scanning Calorimeter) (for example, Thermo Plus 2 manufactured by Rigaku Corporation). The Tg of component (B) can be adjusted to a desired range by adjusting the type and content of the constituent units that make up component (B) (if component (B) is (meth)acrylic resin, the constituent units derived from (meth)acrylic acid ester).

[0039] The weight average molecular weight (Mw) of component (B) 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. When the Mw of component (B) is within such a range, film formability, film strength, flexibility, tackiness, etc. can be appropriately controlled, and at the same time, it has excellent reflow properties and can improve embedability.

[0040] In this specification, the weight average molecular weight (Mw) means a value measured by gel permeation chromatography (GPC) and converted using a calibration curve with standard polystyrene. When multiple peaks are observed in GPC, the weight average molecular weight resulting from the peak with the highest peak intensity is defined as the weight average molecular weight in this specification.

[0041] Commercially available products of component (B) include SG-P3, SG-80H (both manufactured by Nagase ChemteX Corporation), KH-CT-865 (manufactured by Resonac Co., Ltd.), etc.

[0042] As another example of component (B), for example, a (meth)acrylate polymer containing a structural unit derived from a (meth)-acrylate having an epoxy group and satisfying at least one of condition A, condition B, and condition C (hereinafter, may be simply referred to as “(meth)acrylate polymer”). By using a (meth)acrylate polymer as component (B), the crosslink density after curing is dramatically improved, suppressing chip cracking during wire bonding (that is, having excellent wire bonding properties), and there is a tendency to obtain the effect of improving the processability during film cutting (for example, film cutting property for die-cutting into a circular shape). The (meth)acrylate polymer may satisfy at least two of condition A, condition B, and condition C, or may satisfy all of condition A, condition B, and condition C.

[0043] The (meth)acrylate polymer is a (meth)acrylate polymer containing a structural unit derived from a (meth)acrylate having an epoxy group. Examples of the compound that provides a structural unit derived from a (meth)acrylate having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and the like. Among these, the compound that provides a structural unit derived from a (meth)acrylate having an epoxy group may be glycidyl (meth)acrylate or glycidyl methacrylate.

[0044] (Condition A) The content of the structural unit derived from a (meth)acrylate having an epoxy group is 6% by mass or more based on all the structural units of the (meth)acrylate polymer. When the content of the structural unit derived from a (meth)acrylate having an epoxy group is 6% by mass or more based on all the structural units of the (meth)acrylate polymer, good processability can be imparted and excellent wire bonding properties can be imparted when applied to a film adhesive. The content of the structural unit derived from a (meth)acrylate having an epoxy group 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, 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, twenty% by mass or less, 18% by mass or less, 16% by mass or less, or fourteen% by mass or less.

[0045] 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 a (meth)acrylate having an epoxy group can be calculated, for example, from the charged amounts of the monomers used in the production of the (meth)acrylate polymer.

[0046] (Condition 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.

[0047] 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.

[0048] (Condition 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)

[0049] 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 0.0500 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.

[0050] 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.

[0051] 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, 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] (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.

[0060] Here, we will describe a method for producing (meth)acrylate polymers by radical polymerization using solution polymerization.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] The content of the (meth)acrylate polymer 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 the (meth)acrylate polymer in component (B) in the adhesive composition when forming a film-like adhesive may be the same as the above range.

[0067] 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 in this range, it tends to have excellent thin-film formation properties, excellent break elongation when a thin film is formed, and can suppress warping of semiconductor devices (semiconductor packages). The content of component (B) may be 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less, based on the total amount of the film-like adhesive. When the content of component (B) is in this range, it tends to be easier to 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 in the above range.

[0068] (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).

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] (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.

[0074] (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.

[0075] Examples of imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole.

[0076] Component (E) may contain 2-phenylimidazole because it readily promotes hardening at low temperatures.

[0077] The film-like adhesive may further contain other components. Examples of other components include pigments, ion capture agents, antioxidants, and so on.

[0078] 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.

[0079] 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.

[0080] 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 20 MPa or more, and may be 25 MPa or more, 30 MPa or more, 35 MPa or more, 40 MPa or more, 45 MPa or more, 50 MPa or more, 55 MPa or more, 60 MPa or more, 65 MPa or more, 70 MPa or more, 75 MPa or more, 80 MPa or more, 85 MPa or more, 90 MPa or more, 95 MPa or more, 100 MPa or more, 105 MPa or more, 110 MPa or more, 115 MPa or more, or 120 MPa or more. When the storage modulus is 20 MPa or more, 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.

[0081] In this specification, the storage modulus at 150°C of a cured product of a film-like adhesive cured at 140°C for 30 minutes can be measured, for example, by the following method: Multiple layers of 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 4 mm wide x 33 mm long, and the laminate is cured at 140°C for 30 minutes 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 used as the storage modulus at 150°C of the film-like adhesive. (Conditions) ・Measurement mode: Tensile ・Chuck distance: 20 mm ・Heating rate: 3°C / min ・Frequency: 10 Hz ・Load: Automatic static load ・Measurement temperature: 30 to 270°C

[0082] 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.

[0083] 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.

[0084] Mixing or kneading can be carried out using conventional agitators, dispersers, three-roll mills, ball mills, and other dispersers, in appropriate combinations.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] [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.

[0089] The dicing film 4 comprises a base layer 2 and an adhesive layer 3 provided on the base layer 2.

[0090] The base layer 2 can use a base film commonly used in the field of dicing films. The base material of the base film is not particularly limited as long as it can be expanded in the cooling and expanding process. Examples of base materials for the base film include polyolefins such as crystalline polypropylene, amorphous polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, low-density linear polyethylene, polyethylene-polypropylene random copolymer, polyethylene-polypropylene block copolymer, polybutene, and polymethylpentene; ethylene-vinyl acetate copolymer; ionomer resin; ethylene-(meth)acrylic acid copolymer; ethylene-(meth)acrylic acid ester (random, alternating) copolymer; ethylene-butene copolymer; ethylene-hexene copolymer; polyurethane; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate; polyimide; polyether ether ketone; polyetherimide; polyamide; fully aromatic polyamide; polyphenylene sulfide; aramid (paper); glass; glass cloth; fluororesin; polyvinyl chloride; polyvinylidene chloride; cellulose resin; and silicone resin. Among these, the base material of the base film may be polypropylene, polyethylene-polypropylene random copolymer, polyethylene-polypropylene block copolymer, ethylene-vinyl acetate copolymer, ionomer resin, or ethylene-(meth)acrylic acid copolymer, from the viewpoint of properties such as Young's modulus, stress relaxation properties, and melting point.

[0091] 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).

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] [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.

[0100] 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).

[0101] 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.

[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 the support member or the 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 dicing the semiconductor wafer to which the adhesive layer has been attached (dicing step); a step of producing a plurality of individualized semiconductor chips with adhesive pieces by expanding the substrate layer under cooling conditions (cooling and expanding step); a step of picking up a first semiconductor chip with adhesive pieces having a first semiconductor chip and a first adhesive piece from among the plurality of individualized semiconductor chips with adhesive pieces from the adhesive layer (pickup step); and a step of bonding the first semiconductor chip with adhesive pieces 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 having a second semiconductor chip and a second adhesive piece from among the plurality of individualized semiconductor chips with adhesive pieces via the second adhesive piece (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.

[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. Dicing can be performed, for example, from the circuit side of the semiconductor wafer according to conventional methods. In this process, methods such as half-cutting, which involves making a half-cut incision in the semiconductor wafer, or stealth dicing, which involves forming and dividing a modified region using a laser, can be employed. Since the adhesive layer of the dicing-die bonding integrated film described above has excellent cooling and division properties, it is preferable to employ stealth dicing. The dicing apparatus used in this process is not particularly limited, and conventionally known apparatuses can be used.

[0110] The cooling and expanding process is a process of expanding the substrate layer of a dicing film under cooling conditions. This makes it possible to obtain multiple individual semiconductor chips with adhesive pieces attached. In the cooling and expanding process, the substrate layer of the dicing film can be expanded (stretched) by pushing up the substrate layer in the inner region of the dicing film with a cooling stage under cooling conditions. These conditions can be set arbitrarily, but for example, the cooling temperature can be -30 to 5°C, the cooling time can be 30 seconds to 5 minutes, the pushing amount can be 5 to 20 mm, and the pushing speed can be 50 to 300 mm / second.

[0111] After the cooling stage is lowered, the adhesive layer on the outer periphery of the semiconductor chip with adhesive attached may be heated with a heater to shrink the inner region of the dicing film (heat shrinking). The heating temperature when heating with the heater may be, for example, 200 to 270°C or 220 to 250°C.

[0112] 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.

[0113] The pickup process involves picking up semiconductor chips with adhesive pieces attached to a dicing / die bonding integrated film while separating the adhesive pieces from each other, in order to detach the adhesive pieces attached to the film. The method of expanding to separate the adhesive pieces attached to each other is not particularly limited, and various conventionally known methods can be employed. For example, one method of separating the adhesive pieces attached to each other is to expand the substrate layer. The expansion may be performed under cooling conditions as needed. The method of pickup is not particularly limited, and various conventionally known methods can be employed. For example, one method involves pushing up individual adhesive pieces attached to semiconductor chips from the dicing / die bonding integrated film side with a needle, and then picking up the pushed-up adhesive pieces attached to semiconductor chips with a pickup device.

[0114] In this case, if the adhesive layer is radiation-curable (e.g., ultraviolet light), the pickup process 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 peel off the semiconductor chip with the adhesive chip attached. As a result, pickup becomes possible without damaging the semiconductor chip with the adhesive chip attached.

[0115] 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 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] The present disclosure will be described below in detail based on examples, but the present disclosure is not limited to these examples.

[0122] [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 22.2% 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.

[0123] <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.

[0124] [(Evaluation of (meth)acrylate polymer)] (Measurement of weight-average molecular weight (Mw)) As a sample for Mw measurement, a solution containing a (meth)acrylate polymer was dissolved in tetrahydrofuran (THF) to prepare a 0.2 mass% THF solution. Mw was measured by gel permeation chromatography (GPC) method and derived by conversion using a calibration curve of standard polystyrene. The conditions of GPC are shown below. The results are also shown in Table 1. Measurement apparatus: SHODEX (registered trademark) GPC-101 (manufactured by Resonac Co., Ltd.) Detector: Differential refractometer SHODEX RI-71S (manufactured by Resonac Co., Ltd.) Column: SHODEX LF-804 + LF-804 (manufactured by Resonac Co., Ltd.) 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 an indicator titration method according to JIS K7236:2009. The results are shown in Table 1.

[0126] (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 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 the obtained spectrum was subjected to atmospheric correction. Then, the spectrum was displayed with the absorbance on the vertical axis and the wave number (cm －１ ) on the horizontal axis. In the displayed spectrum, the wave numbers of two points corresponding to the minimum values of the absorbance in the range of 880 cm －１ and 927 cm －１ were determined, and the straight line connecting the two points of the wave numbers on the spectrum was used as the baseline. 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 absorbance at 1661 cm －１ and 1842 cm －１ on the spectrumA 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)) originating 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-like Adhesives] <Examples 1-6 and Comparative Examples 1 and 2> (Preparation of Adhesive Varnishes) Adhesive varnishes for Examples 1-6 and Comparative Examples 1 and 2 were prepared by using each component shown in Table 2 in the respective amounts (unit: parts by mass) shown in Table 2. Specifically, cyclohexanone was added to a mixture consisting of component (A) (components (A1) and (A2)) and, if necessary, component (C), and the mixture was 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 for Examples 1-6 and Comparative Examples 1 and 2. Note that each component shown in Table 2 refers to the following, and the values ​​shown in Table 2 refer to parts by mass of the component (solid content) excluding solvents, etc.

[0129] (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)

[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) (A2-2) MEH-7800M (product name, manufactured by Meiwa Chemical Co., Ltd. (now UBE Co., Ltd.), phenylaralkyl-type phenolic resin, hydroxyl group equivalent: 174 g / eq, softening point: 82°C)

[0131] (B) Components: Elastomer (B-1) SG-P3 (product name, manufactured by Nagase ChemteX Corporation, (meth)acrylic rubber 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) (B-2) (meth)acrylate polymer of Production Example 1 (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) (B-3) (meth)acrylate polymer from Production Example 2 (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)

[0132] (C) Ingredients: Inorganic filler (C-1) Aerosil R972 (Trade name ("Aerosil" is a registered trademark), manufactured by Nippon Aerosil Co., Ltd., silica particles, average particle size: 16 nm)

[0133] (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)

[0134] (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)

[0135] (Preparation of film-like adhesives) The adhesive varnishes of Examples 1-6 and Comparative Examples 1 and 2 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 degassed adhesive varnish 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 1-6 and Comparative Examples 1 and 2 with a thickness of 3 μm in the B-stage state. In the film-like adhesives of Examples 1-6 and Comparative Examples 1 and 2, the thickness of the film-like adhesive was adjusted by the amount of adhesive varnish applied.

[0136] [Evaluation of Film-Like Adhesives] <Measurement of Shear Viscosity> The shear viscosity at 120°C was measured using the film-like adhesives of Examples 1 to 6 and Comparative Examples 1 and 2. The shear viscosity at 120°C was measured by the following method. Multiple layers of the film-like adhesive were laminated on a 70°C hot plate using a rubber roll to obtain a laminate with a thickness of 300 to 400 μm. The obtained laminate was cut to a size of φ9 mm to prepare a sample for measurement. The sample was mounted on a measuring jig of a rotary viscoelasticity measuring device (ARES-G2, manufactured by T.A. Instrument Japan Co., Ltd.), and the viscoelasticity of the sample was measured under the following conditions. From the measurement results, the viscosity (complex viscosity ratio) at 120°C was read and used as the shear viscosity of the film-like adhesive at 120°C. The results are shown in Table 2. (Conditions) • Measurement jig: Parallel plate, aluminum, φ8mm • Frequency: 1Hz • Heating rate: 5℃ / min • Strain: 5% • Measurement temperature: 35~180℃

[0137] <Evaluation of Cooling Dissociation Properties> (Preparation of Integrated Dicing and Die Bonding Films) A dicing film comprising a base layer and an adhesive layer was prepared by applying an ultraviolet-curing adhesive to a resin film (thickness: 100 μm, diameter: 370 mm) made of ionomer resin. Next, film-like adhesives with support films (thickness: 3 μm, diameter: 312 mm) of Examples 1 to 6 and Comparative Examples 1 and 2 were prepared, and the adhesive layer of the dicing film and the film-like adhesive were bonded together so that they were in contact, thereby preparing integrated dicing and die bonding films of Examples 1 to 6 and Comparative Examples 1 and 2, comprising a base layer, an adhesive layer, and an adhesive layer (film-like adhesive) in this order.

[0138] (Evaluation of cooling and discontinuity) A semiconductor wafer with a thickness of 50 μm and a diameter of 300 mm was prepared. Using a stealth dicing laser saw (Disco Corporation, device name: DFL7361), a modified layer was formed on the semiconductor wafer to obtain a semiconductor chip of 4 mm x 12 mm. Next, backgrinding was performed using a backgrinding device (Disco Corporation, device name: DGP8761) to thin the semiconductor wafer to a thickness of 30 μm. The support films of the dicing and die bonding integrated films of Examples 1 to 6 and Comparative Examples 1 and 2 were peeled off, and the adhesive layer (film adhesive) of the dicing and die bonding integrated film was laminated onto the semiconductor wafer thinned to a thickness of 30 μm using a laminating device (Disco Corporation, device name: DFM2800) at 70°C. A semiconductor wafer with an integrated dicing and die bonding film attached was fixed, and the dicing film was stretched using an expander (Disco Corporation, device name: DDS2300) under the following conditions by cooling and expanding, thereby separating the adhesive layer and semiconductor wafer into 4 mm x 12 mm semiconductor chips with adhesive layers. Subsequently, the dicing film was shrunk by heating under the following heating conditions (heat shrinking). The separated semiconductor chips were observed, and if the percentage of chips where both the adhesive layer and semiconductor wafer were cut simultaneously was 90% or more, it was evaluated as "A" for good cooling and discontinuity, and if it was less than 90%, it was evaluated as "B" for poor cooling and discontinuity. The results are shown in Table 2. (Cooling and expanding conditions) - Cooling temperature: -15°C - Cooling time: 90 seconds - Push-up amount: 9 mm - Push-up speed: 200 mm / second - Holding time after push-up: 0 seconds (Heating conditions) - Heater temperature: 220°C - Heater rotation speed: 7° / second - Push-up amount: 7 mm - Tape cooling waiting time: 15 seconds

[0139] <Measurement of Storage Modulus> The storage modulus after curing was measured using the film-like adhesives of Examples 1-6 and Comparative Examples 1 and 2. The storage modulus after curing was measured by the following method. Multiple layers of the film-like adhesive were laminated on a 70°C hot plate using a rubber roll to obtain a laminate with a thickness of 160-200 μm. The obtained laminate was cut to a size of 4 mm wide x 33 mm long, and the laminate was cured at 140°C for 30 minutes 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 Table 2. The larger the value of the storage modulus at 150°C (for example, 20 MPa or more), the better it can cover the brittleness of the semiconductor chip due to thinning, and as a result, it tends to suppress the occurrence of chip cracks and have excellent wire bonding properties. (Conditions) ・Measurement mode: Tensile ・Chuck distance: 20 mm ・Heating rate: 3°C / min ・Frequency: 10 Hz ・Load: Automatic static load ・Measurement temperature: 30-270°C

[0140]

[0141] As shown in Table 2, the film-like adhesives of the examples, which had a shear viscosity of 10,000 Pa·s or less at 120°C, were superior in terms of cooling discontinuity compared to the film-like adhesives of the comparative examples, which had a shear viscosity of more than 10,000 Pa·s at 120°C. These results confirm that the film-like adhesive of the present disclosure has excellent cooling discontinuity.

[0142] 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

A film-like adhesive containing a thermosetting resin component and an elastomer, and which may further contain an inorganic filler, The inorganic filler content is 0 to 5% by mass, based on the total amount of the film-like adhesive. The shear viscosity at 120°C is 10,000 Pa·s or less. Film-type adhesive. 　 The content of the thermosetting resin component is 40% by mass or more, based on the total amount of the film-like adhesive. The film-like adhesive according to claim 1. 　 The thermosetting resin component includes an epoxy resin and a phenolic resin. The film-like adhesive according to claim 1. 　 The elastomer content is 30% by mass or more, based on the total amount of the film-like adhesive. The film-like adhesive according to claim 1. 　 The storage modulus of the cured product at 150°C is 20 MPa or higher when the film-like adhesive is cured at 140°C for 30 minutes. The film-like adhesive according to claim 1. 　 The thickness is 15 μm or less. The film-like adhesive according to claim 1. 　 Used in the manufacturing process of semiconductor devices that consist of multiple semiconductor chips stacked on top of each other, The film-like adhesive according to claim 1. 　 The device comprises, 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 6. Dicing and die bonding integrated film. 　 The first semiconductor chip, A support member on which the first semiconductor chip is mounted, A cured film-like adhesive according to any one of claims 1 to 6, provided between the first semiconductor chip and the support member, for bonding the first semiconductor chip and the support member, Equipped with, Semiconductor equipment. 　 The present invention further comprises a second semiconductor chip, which is different from the first semiconductor chip, stacked on the surface of the first semiconductor chip. The semiconductor device according to claim 9. 　 A step of attaching the adhesive layer of the dicing-die bonding integrated film according to claim 8 to a semiconductor wafer, A step of dicing the semiconductor wafer to which the adhesive layer has been attached, A step of producing a plurality of individualized semiconductor chips with adhesive pieces attached by expanding the substrate layer under cooling conditions, A step of picking up a first semiconductor chip having a first adhesive piece from the plurality of individualized semiconductor chips with adhesive pieces, from the adhesive layer, A step of bonding the semiconductor chip with the first adhesive piece to a support member via the first adhesive piece, Equipped with, A method for manufacturing a semiconductor device. 　 The process for manufacturing the adhesive-attached semiconductor chip includes the steps of expanding the substrate layer under cooling conditions and heating the adhesive layer on the outer periphery of the adhesive-attached semiconductor chip to shrink the adhesive layer and the substrate layer on the inner side of the outer periphery. A method for manufacturing a semiconductor device according to claim 11. 　 The process further comprises a step of bonding a second semiconductor chip, which has a second semiconductor chip and a second adhesive piece, to the surface of the first semiconductor chip bonded to the support member, via the second adhesive piece, from among the plurality of individualized semiconductor chips with adhesive pieces. A method for manufacturing a semiconductor device according to claim 11.

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