Resin composition, laminate, semiconductor chip with resin composition layer, substrate for mounting semiconductor chip with resin composition layer, and semiconductor device

Abstract

To provide a resin composition, a laminate, a semiconductor chip with a resin composition layer, a substrate for mounting a semiconductor chip with a resin composition layer, and a semiconductor device which are excellent in low void property, chip adhesion, and moisture absorption heat resistance.SOLUTION: A resin composition is provided, including one or more compounds (A) selected from a group consisting of a maleimide compound (AA) and a citraconimide compound (AB), an allylphenol compound (B), and an inorganic filler (C), and satisfying at least the following (i) and / or (ii). (i) Minimum melt viscosity obtained by measuring melt viscosity under conditions of a measurement start temperature of 40°C, a raised temperature of 10°C / min, a frequency of 10.0 rad / sec and a strain of 0.1% in the range of 40-260°C using a rheometer is 100 Pa s or less. (ii) Viscosity at 200°C when the viscosity is measured under conditions of a measurement start temperature of 40°C, a raised temperature of 10°C / min, a frequency of 10.0 rad / sec and a strain of 0.1% using a rheometer is 400 Pa s or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition, a laminate, a semiconductor chip with a resin composition layer, a semiconductor chip mounting substrate with a resin composition layer, and a semiconductor device. More specifically, the present invention relates to a resin composition useful as an underfill material. [Background technology]

[0002] In recent years, with the miniaturization and high performance of semiconductor devices, flip chip mounting has been attracting attention as a method for mounting a semiconductor chip (hereinafter sometimes abbreviated as "chip") on a semiconductor chip mounting substrate (hereinafter sometimes abbreviated as "substrate"). In flip chip mounting, a typical method is to bond the chip and the substrate, fill the gap between the chip and the substrate with an underfill material, and then harden the material. There is also a method in which the chip or the substrate is filled with an underfill material (also called a pre-applied underfill material), and then the chip, the underfill material, and the substrate are bonded to each other.

[0003] The underfill material is usually further cured in a post-cure process carried out after flip-chip mounting, and then incorporated into the semiconductor device.

[0004] In flip chip mounting and post-cure processes, an important characteristic required of an underfill material is that it must maintain insulation reliability. To achieve this, it is necessary to prevent voids (air bubbles) from forming between the underfill material and the chip or substrate during the process of manufacturing a semiconductor device, and to suppress peeling of the cured underfill material from the chip and substrate.

[0005] After the semiconductor device is manufactured, a motherboard or the like is usually further bonded to the semiconductor device via solder balls or the like. This process usually includes a reflow process for melting the solder balls. The reflow process is usually performed at a high temperature of 240° C. or more.

[0006] Patent Document 1 describes an underfill material that uses a radically polymerizable monomer as the main resin, and describes the incorporation of a silane coupling agent to improve adhesion to the chip. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 2015-503220 Summary of the Invention [Problem to be solved by the invention]

[0008] However, radical polymerizable monomers generally cure quickly, and therefore cure before the formation of bonds between the reactive sites of the silane coupling agent and the silanol groups on the chip surface reaches a sufficient amount. Therefore, the underfill material described in Patent Document 1 does not provide sufficient adhesion and bonding between the resin composition and the chip and substrate, and as a result, voids tend to occur. In addition, since the resin composition cures before filling the unevenness present on the surfaces of the chip and substrate, the underfill material described in Patent Document 1 also has the problem of not providing a sufficient anchor effect that contributes to adhesion.

[0009] Furthermore, if the underfill material contains a large amount of volatile components, there is a problem in that many voids are generated after flip chip mounting or after a post-cure process.

[0010] Furthermore, because semiconductor devices are exposed to high temperatures during the reflow process, if the underfill material has poor moisture absorption and heat resistance, problems arise such as the evaporation of moisture absorbed in the semiconductor device, the expansion and deformation of the underfill material due to high temperatures, the generation of voids in the semiconductor device, and the generation of peeling at the interface between the chip and the underfill material or the interface between the underfill material and the substrate. Therefore, in the field of electronic materials, which requires extremely high insulation reliability, an underfill material with excellent moisture absorption and heat resistance is required.

[0011] The present invention has been made in consideration of such problems, and an object of the present invention is to provide a resin composition, a laminate, a semiconductor chip with a resin composition layer, a semiconductor chip mounting substrate with a resin composition layer, and a semiconductor device, which have excellent low void properties, chip adhesion, and moisture absorption heat resistance. [Means for solving the problem]

[0012] Means of Solving the Problems The present inventors have conducted extensive research to solve the above problems associated with the conventional techniques, and as a result have found that a specific resin composition can solve the above problems, thereby completing the present invention.

[0013] That is, the present invention includes the following. [1] A resin composition comprising one or more compounds (A) selected from the group consisting of maleimide compounds (AA) and citraconic imide compounds (AB), an allylphenol compound (B), and an inorganic filler (C), and which satisfies at least the following (i) and / or (ii): (i) Using a rheometer, the melt viscosity is measured in the range of 40 to 260°C under conditions of a measurement starting temperature of 40°C, a heating rate of 10°C / min, a frequency of 10.0 rad / sec, and a strain of 0.1%, and the minimum melt viscosity obtained is 100 Pa s or less. (ii) The viscosity at 200°C is 400 Pa s or less when measured using a rheometer under conditions of a starting temperature of 40°C, a heating rate of 10°C / min, a frequency of 10.0 rad / sec, and a strain of 0.1%.

[0014] [2] The resin composition according to [1], wherein the maleimide compound (AA) comprises at least one selected from the group consisting of 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, a maleimide compound represented by the following formula (1), a maleimide compound represented by the following formula (2), a maleimide compound represented by the following formula (3), a bismaleimide compound comprising a structural unit represented by the following formula (4) and maleimide groups at both ends of the molecular chain, a maleimide compound represented by the following formula (5), and a maleimide compound represented by the following formula (6).

[0015] [ka]

[0016] (In formula (1), R 8 R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 9 each independently represents a hydrogen atom or a methyl group.

[0017] [ka]

[0018] (In formula (2), R 5 R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 6 each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a -COOR group (R represents an alkyl group having 1 to 6 carbon atoms), or a hydrogen atom. 2 indicates an integer of 1 or greater.)

[0019] [ka]

[0020] (In formula (3), n 3 represents an integer from 1 to 30.

[0021] [ka]

[0022] (In formula (4), R 11 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 12 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 13 Each of n independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. 5 represents an integer from 1 to 10.

[0023] [ka]

[0024] (In formula (5), R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 4 represents an integer from 1 to 10.

[0025] [ka]

[0026] (In formula (6), R 10 Each independently represents a hydrogen atom or a methyl group. 5 indicates an integer greater than or equal to 1.

[0027] [3] The resin composition according to [1] or [2], wherein the maleimide compound (AA) contains a maleimide compound having a structural unit represented by the following formula (7) at an intramolecular end:

[0028] [ka]

[0029] (In formula (7), R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent, and at least one R 8 R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. -* represents a hydrogen atom or a bond.

[0030] [4] The resin composition according to [2], wherein the maleimide compound (AA) comprises at least one selected from the group consisting of the maleimide compound represented by the formula (1) and the maleimide compound represented by the formula (3).

[0031] [5] The compound (A) includes a compound (A1) and a compound (A2), the compound (A1) being one or more selected from the group consisting of a maleimide compound (AA-1) having a weight average molecular weight of 3,000 to 9,500 and a citraconic imide compound (AB-1) having a weight average molecular weight of 3,000 to 9,500, the compound (A2) being one or more selected from the group consisting of a maleimide compound (AA-2) having a weight average molecular weight of 300 to less than 3,000 and a citraconic imide compound (AB-2) having a weight average molecular weight of 300 to less than 3,000, and each of the weight average molecular weights being a value calculated in terms of standard polystyrene by a GPC (gel permeation chromatography) method. The resin composition according to any one of [1] to [4].

[0032] [6] The resin composition according to any one of [1] to [5], wherein the allylphenol compound (B) comprises an allylphenol compound (B1) represented by the following formula (8):

[0033] [ka]

[0034] In formula (8), W represents a divalent organic group having 1 to 15 carbon atoms which may have a substituent. 1 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aldehyde group, or a carboxy group, and n represents an integer of 1 or more.

[0035] [7] The resin composition according to [6], wherein the allylphenol compound (B1) contains an allylphenol compound (B2) represented by the following formula (9):

[0036] [ka]

[0037] (In formula (9), R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and n represents an integer of 1 or more.

[0038] [8] The resin composition according to any one of [1] to [7], wherein a functional group equivalent ratio between the compound (A) and the allylphenol compound (B) ((equivalent of maleimide group in compound (A)+equivalent of citraconic imide group in compound (A)) / equivalent of allyl group in allylphenol compound (B)) is 1 to 4.

[0039] [9] The resin composition according to any one of [1] to [8], wherein the inorganic filler (C) comprises one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide.

[0040]

[10] The resin composition according to any one of [1] to [9], wherein the inorganic filler (C) has an average particle size of 3 μm or less.

[0041]

[11] The resin composition according to any one of [1] to

[10] , wherein the content of the inorganic filler (C) is 10 to 500 parts by mass per 100 parts by mass of the total of the compound (A) and the allylphenol compound (B).

[0042]

[12] The resin composition according to any one of [1] to

[11] , further comprising a flux activator (D).

[0043]

[13] The resin composition according to

[12] , wherein the flux activator (D) contains a rosin-based resin.

[0044]

[14] The resin composition according to any one of [1] to

[13] , which is for use as an underfill material.

[0045]

[15] A laminate comprising a supporting substrate and a layer containing the resin composition according to any one of [1] to

[14] laminated on the supporting substrate.

[0046]

[16] The laminate according to

[15] , wherein the layer containing the resin composition has a thickness of 5 to 500 μm.

[0047]

[17] A semiconductor chip with a resin composition layer, comprising: a semiconductor chip; and a layer containing the resin composition according to any one of [1] to

[14] , laminated on the semiconductor chip.

[0048]

[18] A substrate for mounting a semiconductor chip with a resin composition layer, comprising: a substrate for mounting a semiconductor chip; and a layer containing the resin composition according to any one of [1] to

[14] laminated on the substrate for mounting a semiconductor chip.

[0049]

[19] A semiconductor device comprising a semiconductor chip having a resin composition layer according to

[17] and / or a semiconductor chip mounting substrate having a resin composition layer according to

[18] . Effect of the Invention

[0050] According to the present invention, it is possible to provide a resin composition, a laminate, a semiconductor chip with a resin composition layer, a semiconductor chip mounting substrate with a resin composition layer, and a semiconductor device, which have excellent low void properties, chip adhesion, and moisture absorption and heat resistance. [Brief description of the drawings]

[0051] [Figure 1] FIG. 1 is a rheometer chart obtained by measuring the resin composition layer obtained in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0052] Hereinafter, an embodiment for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described. Note that the following present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment.

[0053] In the present embodiment, "(meth)acryloxy" means both "acryloxy" and the corresponding "methacryloxy", "(meth)acrylonitrile" means both "acrylonitrile" and the corresponding "methacrylonitrile", and "(meth)acrylic" means both "acrylic" and the corresponding "methacrylic".

[0054] In this embodiment, unless otherwise specified, the "resin solid content" or the "resin solid content in the resin composition" refers to the components in the resin composition excluding the inorganic filler (C), the curing catalyst, the silane coupling agent, the wetting dispersant, the additives, and the solvent, and "100 parts by mass of the resin solid content in the resin composition" refers to the total of the components in the resin composition excluding the inorganic filler (C), the curing catalyst, the silane coupling agent, the wetting dispersant, the additives, and the solvent being 100 parts by mass.

[0055] [Resin composition] The resin composition of the present embodiment is a resin composition (also referred to as a curable resin composition in this embodiment) that contains one or more compounds (A) (hereinafter also referred to as simply "compound (A)") selected from the group consisting of maleimide compounds (AA) (hereinafter also referred to as simply "compound (AA)") and citraconic imide compounds (AB) (hereinafter also referred to as simply "compound (AB)"), an allylphenol compound (B) (hereinafter also referred to as simply "compound (B)"), and an inorganic filler (C), and satisfies at least the following (i) and / or (ii). (i) Using a rheometer, the melt viscosity is measured in the range of 40 to 260°C under conditions of a measurement starting temperature of 40°C, a heating rate of 10°C / min, a frequency of 10.0 rad / sec, and a strain of 0.1%, and the minimum melt viscosity obtained is 100 Pa s or less. (ii) The viscosity at 200°C is 400 Pa s or less when measured using a rheometer under conditions of a starting temperature of 40°C, a heating rate of 10°C / min, a frequency of 10.0 rad / sec, and a strain of 0.1%. The resin composition of the present embodiment, being configured as described above, has excellent low void properties, chip adhesion, and moisture absorption and heat resistance. Because the resin composition of the present embodiment has such properties, it is suitable for use as an underfill material for flip chip mounting.

[0056] The resin composition of the present embodiment may further contain a flux activator (D).

[0057] The reason why a resin composition having excellent low void properties, chip adhesiveness, and moisture absorption and heat resistance is obtained in this embodiment is not clear, but the present inventors presume as follows. Usually, polymerization of only maleimide compounds and / or citraconic imide compounds requires high temperatures of 250°C or more, and it is difficult to obtain a sufficient crosslinked structure in the post-cure process. Therefore, in order to increase the reactivity of a resin composition mainly composed of maleimide compounds and / or citraconic imide compounds, it is common to add a thermal radical initiator such as an organic peroxide or an anionic polymerization catalyst such as imidazole. However, when these polymerization catalysts are included, the curing reaction of the resin composition tends to proceed excessively and thicken due to the action of the polymerization catalyst caused by heat during flip-chip mounting. Therefore, it is not possible to discharge voids generated during flip-chip mounting out of the system, and it is difficult to sufficiently remove voids remaining after flip-chip mounting in the post-cure process. Furthermore, maleimide compounds and / or citraconic imide compounds have few polar functional groups, so sufficient chip adhesion cannot be obtained, making it difficult to prevent voids caused by the evaporation of absorbed water during reflow and peeling of the resin composition from the chip and substrate due to heat.

[0058] In contrast, the resin composition of the present embodiment contains one or more compounds (A) selected from the group consisting of maleimide compounds (AA) and citraconic imide compounds (AB), an allylphenol compound (B), and an inorganic filler (C), and has a minimum melt viscosity at 40 to 260°C of 100 Pa s or less, a viscosity at 200°C of 400 Pa s or less, or both. Here, the allyl group contained in the allylphenol compound (B) and the maleimide group and / or citraconimide group contained in the compound (A) undergo an Ene reaction as an initiating reaction, and the Diels-Alder reaction proceeds well even at a relatively low temperature of about 180°C. Therefore, the resulting cured product can have a high crosslink density, a high glass transition point (Tg), and tends to be excellent in heat resistance. This reaction proceeds better in a system containing more compound (A) than allylphenol compound (B).

[0059] As mentioned above, the Ene reaction and the Diels-Alder reaction start at a relatively low temperature of about 180° C. However, since these reactions are sequential reactions, the reaction rates are relatively slow, and the resin composition does not harden much during the short heating period required for flip chip mounting, so it tends not to thicken. In addition, since the resin composition of the present embodiment has a minimum melt viscosity and / or viscosity within a specific range, it is possible to maintain a low viscosity during flip chip mounting, and it is possible to make the resin composition adhere to the chip or substrate while discharging voids caused by volatile components from the resin composition or substrate generated by heat during flip chip mounting to the outside of the system. Therefore, it is presumed that the voids after mounting can be reduced.

[0060] Furthermore, in the resin composition of the present embodiment, since the minimum melt viscosity and / or viscosity are in a specific range, the viscosity is low even after flip chip mounting, and the resin composition can melt and flow again by the heat of the post-cure process. Therefore, it is presumed that the voids remaining after flip chip mounting can be efficiently removed by using pressurized curing or the like. In addition, the Ene reaction and Diels-Alder reaction can be sufficiently promoted even by heating for a long time in the post-cure process, for example, at 200°C for 2 hours. As a result, the obtained cured product can have a higher crosslink density, a higher glass transition point (Tg), and tends to be more excellent in heat resistance.

[0061] In addition, the resin composition of the present embodiment has polar groups such as phenolic hydroxyl groups derived from the allylphenol compound (B), and the polar groups are contained in large amounts in the cured product even after curing. Therefore, even after curing, good chemical bonds are formed between these polar groups and the silanol groups on the chip surface, and the resin composition has an excellent anchor effect on the semiconductor chip and the substrate.

[0062] Furthermore, the resin composition of the present embodiment contains an inorganic filler (C), which provides excellent flame resistance and thermal conductivity, reduces the thermal expansion coefficient and moisture absorption, and tends to provide high moisture absorption heat resistance. In addition, as described above, the resulting cured product has a high crosslink density, so it also tends to have excellent moisture absorption heat resistance. Even after curing, the cured product contains a large amount of polar groups, so it has an excellent anchor effect on the semiconductor chip and the substrate.

[0063] For the above reasons, the resin composition of the present embodiment has excellent low void properties, chip adhesion, and moisture absorption heat resistance, and by using such a resin composition, the adhesion between the resin composition and the chip and substrate is not reduced even after flip chip mounting, after the post-cure process, and after the reflow process, and voids are unlikely to occur. It is presumed that peeling of the cured product from the chip and substrate can be effectively suppressed. However, the reason is not limited to this.

[0064] Next, the minimum melt viscosity and viscosity of the resin composition of the present embodiment will be described, and the method for producing each component and the resin composition will be described later.

[0065] [Resin composition] The resin composition (curable resin composition) of this embodiment is excellent in low voids, chip adhesion, and moisture absorption heat resistance. Therefore, when the resin composition of this embodiment is used as an underfill material in the form of a laminate, preferably as a preapplied underfill material, it is excellent in low voids, chip adhesion, and moisture absorption heat resistance, and also excellent in bonding properties and insulation reliability. Since the resin composition of this embodiment has various excellent characteristics, it is more useful as an underfill material, and even more useful as a preapplied underfill material. The laminate will be described later.

[0066] Since the resin composition of this embodiment is suitable for underfill materials, and more suitable for pre-applied underfill materials, the sheet obtained using the resin composition and the layer containing the resin composition (hereinafter also simply referred to as "resin composition layer") are preferably in a semi-cured state (B stage). Details of the sheet and the resin composition layer will be described later. By the sheet and the resin composition layer being in a semi-cured state, the sheet and the resin composition layer are excellent in low voids, chip adhesion, and moisture absorption heat resistance. In this embodiment, the semi-cured state (B stage) refers to a state in which each component contained in the sheet or the resin composition layer has not actively started to react (cure), but the sheet or the resin composition layer is in a dry state, that is, the sheet or the resin composition layer is heated to a degree that is not sticky, and the state in which the solvent has been volatilized without curing even without heating is also included.

[0067] The resin composition of the present embodiment satisfies at least the above (i) and / or (ii).

[0068] <Minimum melt viscosity> The minimum melt viscosity of the resin composition is preferably 100 Pa·s or less. In this embodiment, the minimum melt viscosity is determined by the above (i). Specifically, the minimum melt viscosity is measured by the following method. That is, the minimum melt viscosity of the resin composition is measured using a rheometer. The rheometer is usually equipped with a heating device. As the heating device, it is preferable to use an electric heater type temperature control module. As an example of the electric heater type temperature control module, there is an electric heater type temperature control module in which HAAKE MARS TM-EL-H (trade name) and Electrical Temperature Module TM-EL-P (trade name) are combined. Furthermore, an upper parallel plate and a measurement table are usually installed in the rheometer. As the upper parallel plate, it is preferable to use an upper parallel plate made of aluminum. The upper parallel plate is usually attached to an adapter. As such an adapter, for example, a ceramic shaft for disposable plates, AdapterP3 (trade name), to which an aluminum disposable upper parallel plate D / PB Al (trade name, plate diameter: 8.0 mm) is attached can be mentioned. As an example of the measurement table, there is an aluminum disposable lower parallel plate TMP25 Al (trade name, 25.0 mm) can be mentioned. The measurement table is usually attached to the electric heater type temperature control module. The minimum melt viscosity is measured in a state where the resin composition is sandwiched between an upper parallel plate and a lower parallel plate. In the measurement, it is preferable to first place the resin composition in the rheometer, and then hold the resin composition in the rheometer at a measurement temperature of 40°C, a pressure of 2N, and a measurement time of 1 minute. Then, the melt viscosity is measured in the range of 40°C to 260°C under the conditions of a measurement start temperature of 40°C, a heating rate of 10°C / min, a frequency of 10.0 rad / sec, and a strain of 0.1%, and the viscosity at which the viscosity is the lowest in the temperature range is defined as the minimum melt viscosity (unit: Pa·s) of the resin composition. It is preferable that the gap (gap) between the upper parallel plate and the lower parallel plate is constant during the measurement. It is also preferable that the resin composition placed on the measurement table has a size of 10 mm (length) x 10 mm (width) x 0.4 to 0.6 mm (thickness) and is in the B stage. The method of making the resin composition into the B stage will be described later. For a specific measurement method, the examples may be referred to. It is to be noted that in this embodiment, the minimum melt viscosity means the viscosity at which the melt viscosity is the lowest in the range of 40 to 260°C.

[0069] The minimum melt viscosity is preferably 85 Pa·s or less, and more preferably 75 Pa·s or less, in order to obtain a resin composition with even more excellent low void properties and chip adhesion. The lower limit is not particularly limited, but in consideration of the use as an underfill material, it is usually 1 Pa·s or more, preferably 5 Pa·s or more, and more preferably 10 Pa·s or more.

[0070] In this embodiment, since the minimum melt viscosity of the resin composition is within the above range, it becomes possible to maintain a low viscosity even during flip chip mounting and at the start of curing in the post-cure process, and there is a tendency that the fluidity of the resin composition in each process can be controlled.

[0071] The minimum melt viscosity of the resin composition can be adjusted to the above range by controlling at least one of the structure and molecular weight of the compound (A) and the compound (B) and the particle size of the inorganic filler (C). The minimum melt viscosity of the resin composition can be more preferably controlled by controlling the respective blending amounts of the compound (A), the compound (B), and the inorganic filler (C).

[0072] In this embodiment, the resin composition used for measuring the minimum melt viscosity is preferably in a B-stage. Examples of methods for making the resin composition into a B-stage include the following methods. That is, an organic solvent, preferably methyl ethyl ketone (MEK), is added to the resin composition containing the compound (A), the compound (B), and the inorganic filler (C) so that the solid content concentration is 40 to 80 mass%, preferably 60 mass%, and the mixture is stirred in a water bath at 20 to 80°C, preferably 70°C, for 10 to 120 minutes, preferably 40 minutes, to obtain a varnish having a solid content concentration of 40 to 80 mass%, preferably 60 mass%. Note that, as the device used for stirring, a known device can be used, but it is preferable to use a high-speed stirring device. Thereafter, the varnish is applied onto a substrate, and the resin composition can be heated and dried at 60 to 160°C, preferably 100°C, for 1 to 60 minutes, preferably 5 minutes, under 0.5 to 2 atm, preferably 1 atm. The resin composition can be made into a B-stage. Note that, in this method, a laminate having a B-staged resin composition as a layer can be obtained. The thickness of the resin composition layer in the laminate is not particularly limited, but is preferably, for example, 5 to 500 μm. As the substrate, a known substrate such as a 38 μm-thick polyethylene terephthalate film coated with a release agent on the surface can be used. For the B-staged resin composition, the examples may be referred to.

[0073] <Viscosity at 200℃> The viscosity of the resin composition at 200° C. is preferably 400 Pa·s or less. In this embodiment, the viscosity at 200° C. is determined by the above (ii). Specifically, the viscosity at 200° C. is measured by the following method. That is, the viscosity of the resin composition at 200° C. is measured using a rheometer. The rheometer is usually equipped with a heating device. As the heating device, it is preferable to use an electric heater type temperature control module. As an example of the electric heater type temperature control module, there is an electric heater type temperature control module in which HAAKE MARS TM-EL-H (trade name) and Electrical Temperature Module TM-EL-P (trade name) are combined. Furthermore, an upper parallel plate and a measurement table are usually installed in the rheometer. As the upper parallel plate, it is preferable to use an upper parallel plate made of aluminum. The upper parallel plate is usually attached to an adapter. As such an adapter, for example, a ceramic shaft for disposable plates, AdapterP3 (trade name), to which an aluminum disposable upper parallel plate D / PB Al (trade name, plate diameter: 8.0 mm) is attached can be mentioned. As an example of the measurement table, there is an aluminum disposable lower parallel plate TMP25 Al (trade name, 25.0 mm) can be mentioned. The measurement table is usually attached to the electric heater type temperature control module. Furthermore, the viscosity at 200° C. is measured in a state where the resin composition is sandwiched between an upper parallel plate and a lower parallel plate. In the measurement, it is preferable to first place the resin composition in the rheometer, and then hold the resin composition in the rheometer at a measurement temperature of 40°C, a pressure of 2N, and a measurement time of 1 minute. Then, the measurement start temperature is set to 40°C, and the viscosity at 200°C is measured under the conditions of a temperature rise rate of 10°C / min, a frequency of 10.0 rad / sec, and a strain of 0.1%, and the value at that time is the viscosity (unit: Pa·s) of the resin composition. It is preferable that the gap (gap) between the upper parallel plate and the lower parallel plate is constant during the measurement. In addition, the resin composition placed on the measurement table has a size of 10 mm (length) x 10 mm (width) x 0.4 to 0.6 mm (thickness), and is preferably in a B-stage. The above may be referred to for the method of B-staging. In addition, the examples may be referred to for a specific measurement method.

[0074] The viscosity at 200°C is preferably 300 Pa·s or less, more preferably 200 Pa·s or less, and even more preferably 150 Pa·s or less, in order to obtain a resin composition with even more excellent low void properties and chip adhesion. The lower limit is not particularly limited, but in consideration of the use as an underfill material, it is usually 1 Pa·s or more, preferably 5 Pa·s or more, and more preferably 10 Pa·s or more.

[0075] In this embodiment, since the viscosity of the resin composition at 200°C is within the above range, it becomes possible to maintain a low viscosity even during flip chip mounting and at the start of curing in the post-cure process, and there is a tendency to be able to control the fluidity of the resin composition in each process.

[0076] The viscosity of the resin composition at 200° C. can be adjusted to the above range by controlling at least one of the structures and molecular weights of the compound (A) and the compound (B) and the particle size of the inorganic filler (C). The viscosity of the resin composition at 200° C. can be more preferably controlled by controlling the respective blending amounts of the compound (A), the compound (B), and the inorganic filler (C).

[0077] In the present embodiment, the resin composition used in the measurement of the viscosity at 200° C. is preferably in a B-stage. As a method for making the resin composition into a B-stage, the method and examples for the resin composition used for the minimum melt viscosity of the above-mentioned resin composition may be referred to.

[0078] Since the resin composition has further excellent low void properties and chip adhesiveness, it is preferable that the resin composition satisfies at least the above condition (ii), and it is more preferable that the resin composition satisfies both the above conditions (i) and (ii).

[0079] Next, each component contained in the resin composition will be described.

[0080] [Compound (A)] The resin composition of the present embodiment contains one or more compounds (B) selected from the group consisting of maleimide compounds (AA) and citraconic imide compounds (AB) in order to obtain a resin composition having excellent reactivity with the allylphenol compound (B) and excellent low void properties, chip adhesiveness, and moisture absorption heat resistance. The compound (A) is not particularly limited as long as it contains one or more groups selected from the group consisting of maleimide groups and citraconic imide groups in the molecule. It is preferable that the compound (A) does not show reactivity with the flux activator (D) described later. The compound (A) can be used alone or in a suitable mixture of two or more types.

[0081] The compound (A) preferably contains a maleimide compound (AA) because it has a tendency to obtain a resin composition having better reactivity with the compound (B) and better low void properties, chip adhesiveness, and moisture absorption and heat resistance. In addition, the maleimide compound (AA) is significantly less likely to react with a flux activator during storage or heat treatment than an epoxy compound, and is less likely to cause deactivation of the flux activator.

[0082] Since there is a tendency to obtain a resin composition having even better reactivity with the compound (B) and even better low voids, chip adhesiveness, and moisture absorption heat resistance, the compound (A) includes the compound (A1) and the compound (A2), and the compound (A1) is one or more selected from the group consisting of the maleimide compound (AA-1) having a weight average molecular weight of 3,000 to 9,500 and the citraconic imide compound (AB-1) having a weight average molecular weight of 3,000 to 9,500, and the compound (A2) is one or more selected from the group consisting of the maleimide compound (AA-2) having a weight average molecular weight of 300 to less than 3,000 and the citraconic imide compound (AB-2) having a weight average molecular weight of 300 to less than 3,000. In this specification, the weight average molecular weight is a value calculated in terms of standard polystyrene by GPC (gel permeation chromatography).

[0083] The resin composition of the present embodiment contains the compounds (A1) and (A2) as the compound (A), and thus has further excellent low void properties, chip adhesiveness, and moisture absorption heat resistance. Although the reason for this is unclear, the present inventors presume as follows. That is, by containing the compound (A1) having a relatively high molecular weight, the stress generated during flip chip mounting and / or curing shrinkage during post-cure, and during expansion and shrinkage during reflow, tends to be alleviated. Therefore, voids are reduced, and the effects of chip adhesion and moisture absorption heat resistance are further promoted. In addition, by containing the compound (A2) having a relatively low molecular weight, the resin composition tends to be able to improve the crosslink density during flip chip mounting and / or post-cure. As a result, it is presumed that voids are reduced, stress relaxation occurs, and the chip adhesion and moisture absorption heat resistance that are manifested with stress relaxation can be further promoted. However, the reason is not limited to this.

[0084] As the compound (A1), it is preferable to include a maleimide compound (AA-1), since this tends to result in a resin composition that is even more excellent in terms of low void properties, chip adhesiveness, and moisture absorption heat resistance.

[0085] As the compound (A2), it is preferable to include a maleimide compound (AA-2), since this tends to result in a resin composition which is even more excellent in terms of low void properties, chip adhesiveness, and moisture absorption heat resistance.

[0086] The maleimide compound (AA-1) has a weight average molecular weight of preferably 3,200 or more and 8,000 or less, and more preferably 3,300 or more and 6,000 or less, since this tends to give a resin composition having even more excellent low void properties, chip adhesiveness, and moisture absorption and heat resistance.

[0087] The weight average molecular weight of the citraconic imide compound (AB-1) is preferably 3,200 or more and 8,000 or less, and more preferably 3,300 or more and 6,000 or less, since this tends to result in a resin composition having even better low void properties, chip adhesion, and moisture absorption and heat resistance.

[0088] The maleimide compound (AA-2) has a weight average molecular weight of preferably 350 or more and 2,800 or less, and more preferably 400 or more and 2,500 or less, since this tends to give a resin composition having even more excellent low void properties, chip adhesiveness, and moisture absorption and heat resistance.

[0089] The weight average molecular weight of the citraconic imide compound (AB-2) is preferably 350 or more and 2,800 or less, and more preferably 400 or more and 2,500 or less, since this tends to result in a resin composition having even better low void properties, chip adhesion, and moisture absorption and heat resistance.

[0090] (Maleimide Compound (AA)) The maleimide compound (AA) is not particularly limited as long as it is a resin or compound having one or more maleimide groups in the molecule. The maleimide compound (AA) can be used alone or in combination of two or more kinds.

[0091] Examples of such maleimide compounds (AA) include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 4,4-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenylether bismaleimide, 4,4-diphenylsulfone bismaleimide, and the like. bis(maleimide), 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, polyphenylmethane maleimide, novolac-type maleimide compounds, biphenylaralkyl-type maleimide compounds, 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, a maleimide compound represented by formula (1), a maleimide compound represented by formula (2), a maleimide compound represented by formula (3), a bismaleimide compound containing a structural unit represented by formula (4) and maleimide groups at both ends of the molecular chain, a maleimide compound represented by formula (5), and a maleimide compound represented by formula (6). The compound (A) can also be contained in the resin composition according to the present embodiment in the form of a prepolymer obtained by polymerizing a maleimide compound, or a prepolymer obtained by polymerizing a maleimide compound with another compound such as an amine compound.

[0092] [ka]

[0093] In formula (1), R 8R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 9 each independently represents a hydrogen atom or a methyl group.

[0094] R 8 In the above, the alkyl group having 1 to 6 carbon atoms may refer to the following: Since the viscosity and reactivity can be more suitably controlled, the alkyl group having 1 to 6 carbon atoms is preferably one or more selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and more preferably a methyl group and / or an ethyl group.

[0095] R 8 In the above, the alkenyl group having 2 to 6 carbon atoms may refer to the following: As the alkenyl group having 2 to 6 carbon atoms, a vinyl group and / or an allyl group are preferred, since they are cured more suitably and a cured product having a higher crosslink density can be obtained.

[0096] R 8 In the above, examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a p-chlorophenyl group, a 2,4-dichlorophenyl group, and a 3-carbamoylphenyl group. The phenyl group which may have a substituent is preferably a phenyl group and / or a p-methylphenyl group, since the viscosity and reactivity can be more suitably controlled.

[0097] Since there is a tendency to obtain a resin composition with even lower voids and better chip adhesion, 8 More preferably, at least one of the groups is a methyl group or an ethyl group.

[0098] Since there is a tendency to obtain a resin composition with even lower voids and better chip adhesion, 9 is more preferably a hydrogen atom.

[0099] The compound represented by formula (1) may be a commercially available product, such as BMI-70 (trade name: bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, maleimide group (functional group) equivalent: 221 g / eq, weight average molecular weight: 550) manufactured by K.I. Chemical Co., Ltd.

[0100] [ka]

[0101] In formula (2), R 5 R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 6 each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a -COOR group (R represents an alkyl group having 1 to 6 carbon atoms), or a hydrogen atom. 2 indicates an integer of 1 or greater.

[0102] R 5 In the above, the alkyl group having 1 to 6 carbon atoms may refer to the following: Since the viscosity and reactivity can be more suitably controlled, the alkyl group having 1 to 6 carbon atoms is preferably one or more selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and more preferably a methyl group and / or an ethyl group.

[0103] R 5 In the above, the alkenyl group having 2 to 6 carbon atoms may refer to the following: As the alkenyl group having 2 to 6 carbon atoms, a vinyl group and / or an allyl group are preferred, since they are cured more suitably and a cured product having a higher crosslink density can be obtained.

[0104] R 5In the above, examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a p-chlorophenyl group, a 2,4-dichlorophenyl group, and a 3-carbamoylphenyl group. The phenyl group which may have a substituent is preferably a phenyl group and / or a p-methylphenyl group, since the viscosity and reactivity can be more suitably controlled.

[0105] Since there is a tendency to obtain a resin composition with even lower voids and better chip adhesion, 5 More preferably, at least one of the groups is a methyl group or an ethyl group.

[0106] R 6 In the above, the alkyl group having 1 to 6 carbon atoms may be linear or branched. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a tert-pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, an n-hexyl group, a 2-hexyl group, a 3-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, and a 2-methylpentan-3-yl group.

[0107] R 6 In the above, the alkoxy group having 1 to 10 carbon atoms may be linear or branched. Examples of such an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, an n-hexanoxy group, and a 2-methylpropoxy group.

[0108] R 6 In the above, the alkyl group having 1 to 6 carbon atoms in the -COOR group may refer to the above.

[0109] n 2is preferably an integer of 1 to 10, and more preferably an integer of 1 to 6.

[0110] The compound represented by formula (2) may be a commercially available product, and examples thereof include a compound represented by formula (11) (BCPH01 (trade name, Mw / Mn: 1.0 to 1.8) manufactured by Gun-ei Chemical Industry Co., Ltd., and BCPH13 (trade name, Mw / Mn: 1.0 to 1.6) manufactured by Gun-ei Chemical Industry Co., Ltd.) and a compound represented by formula (12) (BMCX426 (trade name) manufactured by Gun-ei Chemical Industry Co., Ltd.).

[0111] [ka]

[0112] In formula (11), n 21 is an integer from 1 to 5.

[0113] [ka]

[0114] In formula (12), n 22 is an integer from 1 to 10.

[0115] [ka]

[0116] In formula (3), n 3 represents an integer from 1 to 30.

[0117] The maleimide compound represented by formula (3) may be a commercially available product. For example, BMI-1000P (trade name, n in formula (3)) manufactured by K.I. Chemical Co., Ltd. may be used. 3 = 14 (average value), maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700), BMI-650P (trade name, manufactured by K.I. Chemicals Co., Ltd., n in formula (3) 3 = 9 (average value)), BMI-250P (trade name, n in formula (3)) manufactured by K.I. Chemical Co., Ltd.3 = 3 to 8 (average value)), CUA-4 (trade name, n in formula (3)) manufactured by KI Chemical Co., Ltd. 3 =1) are mentioned.

[0118] [ka]

[0119] In formula (4), R 11 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 12 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 13 Each of n independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. 5 represents an integer from 1 to 10. The constitutional unit represented by formula (4) will be described in detail later.

[0120] As the bismaleimide compound containing a constituent unit represented by formula (4) and maleimide groups at both ends of the molecular chain, a commercially available product may be used, and an example thereof includes MIZ-001 (trade name, containing a maleimide compound represented by formula (13), maleimide group (functional group) equivalent: 800 g / eq, weight average molecular weight: 3900) manufactured by Nippon Kayaku Co., Ltd.

[0121] [ka]

[0122] In the formula (13), a represents an integer of 1 to 10. The maleimide compound represented by the formula (13) may be a mixture of compounds having different a's.

[0123] [ka]

[0124] In formula (5), R 7 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 4 represents an integer from 1 to 10.

[0125] R 7 In the above, reference may be made to the alkyl group having 1 to 6 carbon atoms. In order to more suitably control the viscosity and reactivity, the alkyl group having 1 to 6 carbon atoms is preferably at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and more preferably a methyl group and / or an ethyl group.

[0126] R 7 In the above, the alkenyl group having 2 to 6 carbon atoms may refer to the following: As the alkenyl group having 2 to 6 carbon atoms, a vinyl group and / or an allyl group are preferred, since they are cured more suitably and a cured product having a higher crosslink density can be obtained.

[0127] R 7 In the above, examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a p-chlorophenyl group, a 2,4-dichlorophenyl group, and a 3-carbamoylphenyl group. The phenyl group which may have a substituent is preferably a phenyl group and / or a p-methylphenyl group, since the viscosity and reactivity can be more suitably controlled.

[0128] Since there is a tendency to obtain a resin composition with even better low voids, chip adhesiveness, and moisture absorption and heat resistance, 7 is preferably a hydrogen atom.

[0129] As the maleimide compound represented by formula (5), a commercially available product may be used. For example, MIR-3000-70MT (trade name, R 7 are all hydrogen atoms, and n 4The maleimide group (functional group) equivalent is 275 g / eq, and the weight average molecular weight is 1050.

[0130] [ka]

[0131] In formula (6), R 10 Each independently represents a hydrogen atom or a methyl group. 5 indicates an integer of 1 or more. 5 is preferably an integer of 1 to 10. 5 may be an integer greater than or equal to 2.

[0132] An example of the maleimide compound represented by formula (6) is BMI-2300 (trade name, maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500) manufactured by Daiwa Chemical Industry Co., Ltd.

[0133] As the 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane, a commercially available product may be used, for example, BMI-80 (trade name, maleimide group (functional group) equivalent: 285 g / eq, molecular weight: 570.6) manufactured by K.I. Chemical Co., Ltd.

[0134] Next, the structure of a bismaleimide compound containing a constitutional unit represented by formula (4) and maleimide groups at both ends of the molecular chain will be described. The bismaleimide compound may have a plurality of constitutional units represented by formula (4). In this case, R 11 , R 12 , and R 13 may be the same or different. In addition, the bismaleimide compound has a constitutional unit represented by formula (4), 11 , R 12 , and R 13 and a mixture of compounds in which at least one of the numbers of the constituent units of formula (4) in the bismaleimide compound is different. In the constitutional unit represented by formula (4), R 11 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 11 As the alkylene group, a linear or branched alkylene group is preferable, and a linear alkylene group is more preferable, because the resin composition has a suitable viscosity when the resin composition layer is mounted on a chip or a substrate, and the increase in melt viscosity during mounting can be suitably controlled.

[0135] The number of carbon atoms in the alkylene group is preferably 2 to 14, and more preferably 4 to 12, since the resin composition has a more suitable viscosity when the resin composition layer is mounted on a chip or a substrate, and the increase in melt viscosity during mounting can be more suitably controlled. Examples of linear or branched alkylene groups include methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, undecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, neopentylene, dimethylbutylene, methylhexylene, ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyldodecylene, methylundecylene, methyltridecylene, methyltetradecylene, and methylpentadecylene.

[0136] The number of carbon atoms in the alkenylene group is preferably 2 to 14, and more preferably 4 to 12, from the viewpoint that the resin composition has a more suitable viscosity when the resin composition layer is mounted on a chip or a substrate, and the increase in melt viscosity during mounting can be more suitably controlled. Examples of linear or branched alkenylene groups include vinylene, 1-methylvinylene, propenylene, isopropenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, isopentylene, cyclopentenylene, cyclohexenylene, and dicyclopentadienylene groups.

[0137] In the constitutional unit represented by formula (4), R 12 R represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. 12 As the alkylene group, a linear or branched alkylene group is preferable, and a linear alkylene group is more preferable, because the resin composition has a suitable viscosity when the resin composition layer is mounted on a chip or a substrate, and the increase in melt viscosity during mounting can be suitably controlled.

[0138] The number of carbon atoms in the alkylene group is preferably 2 to 14, and more preferably 4 to 12, since the resin composition has a more suitable viscosity when the resin composition layer is mounted on a chip or a substrate, and the increase in melt viscosity during mounting can be more suitably controlled. The linear or branched alkylene group may be any of the above R 11 You may also refer to:

[0139] The number of carbon atoms in the alkenylene group is preferably 2 to 14, and more preferably 4 to 12, from the viewpoint that the resin composition has a more suitable viscosity when the resin composition layer is mounted on a chip or a substrate, and the increase in melt viscosity during mounting can be more suitably controlled. The linear or branched alkenylene group may be any of the above R 11 You may also refer to:

[0140] In the constitutional unit represented by formula (4), R 11 And, R 12and may be the same or different, but are preferably the same in terms of facilitating the synthesis of the bismaleimide compound.

[0141] In the constitutional unit represented by formula (4), R 13 R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. 13 are preferably each independently a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms, in order that the resin composition has a suitable viscosity when the resin composition layer is mounted on a chip or a substrate, and an increase in melt viscosity during mounting can be suitably controlled; R 13 Among these, 1 to 5 groups (R 13 ) is a linear or branched alkyl group having 1 to 16 carbon atoms, and the remaining groups (R 13 ) is more preferably a hydrogen atom, and R 13 Among these, 1 to 3 groups (R 13 ) is a linear or branched alkyl group having 1 to 16 carbon atoms, and the remaining groups (R 13 ) is more preferably a hydrogen atom.

[0142] The number of carbon atoms in the alkyl group is preferably 2 to 14, and more preferably 4 to 12, since the resin composition has a more suitable viscosity when the resin composition layer is mounted on a chip or a substrate, and the increase in melt viscosity during mounting can be more suitably controlled. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 1-ethylpropyl group, an n-butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a tert-pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, an n-hexyl group, a 2-hexyl group, a 3-hexyl group, an n-heptyl group, an n-octyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 2-methylpentan-3-yl group, and an n-nonyl group.

[0143] The number of carbon atoms in the alkenyl group is preferably 2 to 14, and more preferably 4 to 12, since the resin composition has a more suitable viscosity when the resin composition layer is mounted on a chip or substrate, and the increase in melt viscosity during mounting can be more suitably controlled. Examples of linear or branched alkenyl groups include vinyl, allyl, 4-pentenyl, isopropenyl, isopentenyl, 2-heptenyl, 2-octenyl, and 2-nonenyl groups.

[0144] In the constitutional unit represented by formula (4), n 5 represents an integer from 1 to 10.

[0145] The bismaleimide compound has maleimide groups at both ends of the molecular chain. Both ends mean both ends of the molecular chain of the bismaleimide compound. For example, when the structural unit represented by formula (4) is at the end of the molecular chain of the bismaleimide compound, the maleimide group is represented by the formula: 11 This means that the maleimide group is present at the end of the molecular chain of the maleimide ring, at the end of the molecular chain of the N atom of the maleimide ring, or at both ends. The bismaleimide compound may have a maleimide group in addition to both ends of the molecular chain. The maleimide group is represented by formula (14), and the N atom is bonded to the molecular chain of the bismaleimide compound. The maleimide groups bonded to the bismaleimide compound may all be the same or different, but it is preferable that the maleimide groups at both ends of the molecular chain are the same.

[0146] [ka]

[0147] In formula (14), R 11 R each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. 11 and R 1 and R 2 are preferably hydrogen atoms since they can react more suitably with compound (B). The number of carbon atoms in the alkyl group is preferably 1 to 3, and more preferably 1 or 2, in terms of enabling a more favorable reaction with compound (B). As the linear or branched alkyl group, the above R 13 You may also refer to:

[0148] Among the above, the maleimide compound (AA) is preferably 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, a maleimide compound represented by formula (1), a maleimide compound represented by formula (2), a maleimide compound represented by formula (3), It is preferable that the copolymer contains at least one selected from the group consisting of a maleimide compound, a bismaleimide compound containing a structural unit represented by formula (4) and maleimide groups at both ends of the molecular chain, a maleimide compound represented by formula (5), and a maleimide compound represented by formula (6), and it is more preferable that the copolymer contains at least one selected from the group consisting of 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane, a maleimide compound represented by formula (1), a maleimide compound represented by formula (3), a maleimide compound represented by formula (5), and a maleimide compound represented by formula (6).

[0149] In view of obtaining a resin composition having even better reactivity with compound (B) and even better low void properties, chip adhesion, and moisture absorption heat resistance, the maleimide compound (AA) preferably contains one or more selected from the group consisting of the maleimide compound represented by formula (1) and the maleimide compound represented by formula (3), and more preferably contains both the maleimide compound represented by formula (1) and the maleimide compound represented by formula (3).

[0150] As the maleimide compound (AA-1), a maleimide compound represented by formula (3) (n in formula (3)) is preferred, since it has a higher reactivity with compound (B) and can provide a resin composition having lower voids, chip adhesiveness, and moisture absorption and heat resistance. 3 = 14 (average value, maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700).

[0151] As the maleimide compound (AA-2), from the viewpoint of obtaining a resin composition having even better reactivity with compound (B) and having even better low void properties, chip adhesion, and moisture absorption heat resistance, it is more preferable that the maleimide compound (AA-2) contains one or more selected from the group consisting of 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane, a maleimide compound represented by formula (1), a maleimide compound represented by formula (5), and a maleimide compound represented by formula (6), and it is even more preferable that the maleimide compound (AA-2) contains the maleimide compound represented by formula (1).

[0152] The maleimide compound (AA) preferably includes a maleimide compound containing a constitutional unit represented by formula (7) at an intramolecular terminal.

[0153] [ka]

[0154] In formula (7), R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent, and at least one R 8 R is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. -* represents a hydrogen atom or a bond.

[0155] In this embodiment, when the resin composition contains a maleimide compound containing a structural unit represented by formula (7) at the end of the molecule, the minimum melt viscosity and the viscosity at 200°C tend to be lower. That is, during flip chip mounting, the curing reaction due to the ene reaction with the allyl group contained in the allylphenol compound (B) and the Diels-Alder reaction is unlikely to proceed excessively, and the low viscosity tends to be maintained even more. Therefore, during flip chip mounting, the low viscosity can be more suitably maintained, and the resin composition can be more closely attached to the chip and the substrate while voids caused by volatile components from the resin composition and the substrate generated by heat during mounting are discharged to the outside of the system. As a result, the voids after mounting tend to be reduced.

[0156] Furthermore, since the resin composition can maintain a low viscosity even after flip-chip mounting, it is more likely that the resin composition will melt and flow again due to the heat of the post-cure process. Therefore, by using pressurized curing or the like, the voids generated during flip-chip mounting can be more efficiently removed. In addition, by heating for a long time in the post-cure process, for example at 200°C for 2 hours, the ene reaction and the Diels-Alder reaction can be more fully advanced. This allows the obtained cured product to have a higher crosslink density, a higher glass transition point (Tg), and a tendency to be more excellent in heat resistance. Although the reason for this is unclear, the present inventors speculate as follows.

[0157] That is, the maleimide compound containing the constitutional unit represented by formula (7) at the terminal of the molecule has at least one R 8(At the ortho position of the maleimide) there is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. In this way, the maleimide compound having a substituent at the ortho position has its steric hindrance restricting the movement of the maleimide group, and the reactivity between the maleimide compound and the compound (B) is reduced. Therefore, it is presumed that the minimum melt viscosity and viscosity of the resin composition are further lowered, and the low viscosity can be further maintained even during flip chip mounting and at the start of curing in the post-cure process. Therefore, it is presumed that the above-mentioned effect is obtained. However, the reason is not limited to this.

[0158] In formula (7), when -* represents a bond, it bonds to, for example, an organic group or the main chain of a polymer. The organic group includes a group containing one or more carbon atoms, or a group formed by removing one hydrogen atom from an organic compound.

[0159] R 8 In the above, the alkyl group having 1 to 6 carbon atoms may refer to the above. In order to more suitably control the viscosity and reactivity, the alkyl group having 1 to 6 carbon atoms is preferably at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and more preferably a methyl group and / or an ethyl group.

[0160] R 8 In the above, the alkenyl group having 2 to 6 carbon atoms may refer to the above. As the alkenyl group having 2 to 6 carbon atoms, a vinyl group and / or an allyl group are preferred, since they are cured more suitably and a cured product having a higher crosslink density can be obtained.

[0161] R 8In the above, examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a p-chlorophenyl group, a 2,4-dichlorophenyl group, and a 3-carbamoylphenyl group. The phenyl group which may have a substituent is preferably a phenyl group and / or a p-methylphenyl group, since the viscosity and reactivity can be more suitably controlled.

[0162] R 3 In the above, the alkyl group having 1 to 6 carbon atoms may refer to the above.

[0163] R 3 In the above, the alkenyl group having 2 to 6 carbon atoms may refer to the above.

[0164] R 3 In the above, the optionally substituted phenyl group may refer to the above.

[0165] Since the curing is more favorable and a cured product having a higher crosslink density can be obtained, 3 is preferably a hydrogen atom.

[0166] Since the maleimide compound having a structural unit represented by formula (7) at an end of its molecule preferably includes one or more selected from the group consisting of the maleimide compound represented by formula (1) and the maleimide compound represented by formula (2), it is more preferable that the maleimide compound includes the maleimide compound represented by formula (1), since this leads to more optimal curing and a cured product having a higher crosslink density.

[0167] (Citraconimide Compounds (AB)) Examples of the citraconimide compound (AB) include o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidephenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidephenyl)methane, bis(3,5-diethyl-4-citraconimidephenyl)methane, 1,3-xylylene bis(citraconimide), N-[3-bis(trimethylsilyl)amino-1-propyl]citraconimide, Examples of the citraconimide include N-[3-bis(triethylsilyl)amino-1-propyl]citraconimide, N-[3-bis(triphenylsilyl)amino-1-propyl]citraconimide, N,N'-(m-phenylenedimethylene)dicitraconimide, and N-[3-(methylidenesuccinimidemethyl)benzyl]citraconimide, a citraconimide compound represented by formula (15), a biscitraconimide compound containing a structural unit represented by formula (4) and a citraconimide group at both ends of the molecular chain, a citraconimide compound represented by the following formula (16), a citraconimide compound represented by the following formula (17), and a citraconimide compound represented by the following formula (18). For the biscitraconimide compound, the above-mentioned bismaleimide compound can be referred to. Details of the structural unit represented by formula (4) are as described above, and for the citraconimide group, in the above-mentioned formula (14), R 11 The structure of formula (14) can be seen, except that at least one of the groups is a methyl group. The citraconimide compounds (AB) can be used alone or in combination of two or more.

[0168] From the viewpoint of obtaining a resin composition having even better reactivity with compound (B) and having even better low void properties, chip adhesion, and moisture absorption heat resistance, it is preferable that the citraconic imide compound (AB) includes at least one selected from the group consisting of a citraconic imide compound represented by formula (15), a biscitraconimide compound containing a structural unit represented by formula (4) and citraconic imide groups at both ends of the molecular chain, a citraconic imide compound represented by formula (16) below, a citraconic imide compound represented by formula (17) below, and a citraconic imide compound represented by formula (18) below.

[0169] The citraconic imide compound (AB-1) preferably contains a citraconic imide compound represented by formula (15), since this has better reactivity with the compound (B) and provides a resin composition with better low void properties, chip adhesion, and moisture absorption and heat resistance.

[0170] [ka]

[0171] In formula (15), n 6 represents an integer from 1 to 30.

[0172] As the citraconic imide compound (AB-2), it is preferable to include at least one selected from the group consisting of a citraconic imide compound represented by formula (16), a citraconic imide compound represented by the following formula (17), and a citraconic imide compound represented by the following formula (18), in that a resin composition having even better reactivity with compound (B) and even better low void properties, chip adhesion, and moisture absorption and heat resistance can be obtained.

[0173] [ka]

[0174] In formula (16), R 8R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 9 each independently represents a hydrogen atom or a methyl group. For the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, and the phenyl group which may have a substituent, reference may be made to the above.

[0175] [ka]

[0176] In formula (17), R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. 4 represents an integer of 1 or more, and preferably represents an integer of 1 to 10. For the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, and the phenyl group which may have a substituent, see above. R 10 is preferably a hydrogen atom.

[0177] [ka]

[0178] In formula (18), R 10 Each independently represents a hydrogen atom or a methyl group. 5 indicates an integer of 1 or more. 5 is preferably an integer of 1 to 10. 5 may be an integer greater than or equal to 2.

[0179] In the resin composition of this embodiment, the content of compound (A) is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, and even more preferably 70 to 85 parts by mass, relative to 100 parts by mass of the total of compound (A) and compound (B), in order to obtain a resin composition having even better reactivity with compound (B) and having even better low void properties, chip adhesiveness, and moisture absorption heat resistance.

[0180] In the resin composition of this embodiment, the content of compound (A) is preferably 40 to 95 parts by mass, more preferably 50 to 90 parts by mass, and even more preferably 55 to 85 parts by mass, relative to 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of obtaining a resin composition having even better reactivity with compound (B) and having even better low void properties, chip adhesiveness, and moisture absorption heat resistance.

[0181] When the compound (A) contains the compound (A1) and the compound (A2), the content of the compound (A1) is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 7 to 15 parts by mass, based on 100 parts by mass of the total of the compound (A1) and the compound (A2), in order to obtain a resin composition having better reactivity with the compound (B) and better low voids, chip adhesiveness, and moisture absorption heat resistance. The content of the compound (A2) is preferably 70 to 99 parts by mass, more preferably 80 to 95 parts by mass, and even more preferably 85 to 93 parts by mass, based on 100 parts by mass of the total of the compound (A1) and the compound (A2).

[0182] When the compound (A) contains the compound (AA-1) and the compound (AA-2), the content of the compound (AA-1) is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 7 to 15 parts by mass, based on 100 parts by mass of the total of the compounds (AA-1) and (AA-2), in order to obtain a resin composition having better reactivity with the compound (B) and better low voids, chip adhesiveness, and moisture absorption heat resistance. The content of the compound (AA-2) is preferably 70 to 99 parts by mass, more preferably 80 to 95 parts by mass, and even more preferably 85 to 93 parts by mass, based on 100 parts by mass of the total of the compounds (AA-1) and (AA-2).

[0183] When the compound (A) contains the citraconic imide compound (AB-1) and the citraconic imide compound (AB-2), the reactivity with the compound (B) is more excellent, and the resin composition is more excellent in terms of low voids, chip adhesiveness, and moisture absorption heat resistance. Therefore, the content of the citraconic imide compound (AB-1) is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 7 to 15 parts by mass, relative to 100 parts by mass of the total of the compounds (AB-1) and (AB-2). The content of the citraconic imide compound (AB-2) is preferably 70 to 99 parts by mass, more preferably 80 to 95 parts by mass, and even more preferably 85 to 93 parts by mass, relative to 100 parts by mass of the total of the compounds (AB-1) and (AB-2).

[0184] When compound (A) contains a maleimide compound containing a structural unit represented by formula (7) at an end in the molecule, the amount of the maleimide compound is preferably 10 to 100 parts by mass, more preferably 15 to 95 parts by mass, and even more preferably 20 to 90 parts by mass, relative to 100 parts by mass in total of compound (A), from the viewpoints that the minimum melt viscosity and viscosity can be suitably controlled and a resin composition having even better low void properties, chip adhesiveness, and moisture absorption heat resistance can be obtained.

[0185] [Allylphenol compound (B)] The resin composition of the present embodiment contains an allylphenol compound (B) because it provides excellent reactivity with the compound (A) and provides a resin composition with low voids, chip adhesiveness, and excellent moisture absorption and heat resistance. The allylphenol compound (B) may be a phenol compound or resin having one or more allyl groups in one molecule, and known compounds or resins can be used. In this specification, the allyl group in the allylphenol compound (B) refers to a functional group bonded to an aromatic ring in the main chain, the aromatic ring -CH 2 -CH=CH 2The term "allyl phenol compound" refers to a functional group having the structure of the formula: The phenol compound may, for example, be phenol, bisphenol, or naphthol, and may have a substituent other than an allyl group. The allyl phenol compound (B) may be used alone or in a suitable mixture of two or more kinds.

[0186] The allylphenol compound (B) has a weight average molecular weight of preferably 300 to 10,000, more preferably 500 to 5,000, and even more preferably 750 to 3,000, in that a resin composition having better reactivity with the compound (A) and better low void properties, chip adhesiveness, and moisture absorption and heat resistance can be obtained.

[0187] The allyl phenol compound (B) has an allyl equivalent of preferably 50 to 1200 g / eq., more preferably 100 to 600 g / eq., further preferably 110 to 300 g / eq., and most preferably 120 to 200 g / eq., in order to obtain a resin composition having even better reactivity with the compound (A) and even better low void properties, chip adhesiveness, and moisture absorption and heat resistance. In this specification, the allyl group equivalent is the mass of an allyl phenol compound containing one equivalent of an allyl group. The allyl group equivalent can be, for example, 13 It is measured by C-NMR.

[0188] The allylphenol compound (B) preferably contains an allylphenol compound (B1) represented by the following formula (8), since it provides a resin composition having better reactivity with the compound (A) and better low void properties, chip adhesiveness, and moisture absorption heat resistance.

[0189] [ka]

[0190] In formula (8), W represents a divalent organic group having 1 to 15 carbon atoms which may have a substituent. 1each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aldehyde group, or a carboxy group, and n represents an integer of 1 or more.

[0191] Examples of the divalent organic group having 1 to 15 carbon atoms, which may have a substituent, include linear, branched, or cyclic divalent hydrocarbon groups having 1 to 15 carbon atoms, which may have a substituent. Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, or a divalent linking group formed by combining these. The hydrogen atom in the divalent organic group may be substituted with a halogen atom, an alkoxy group such as a methoxy group and a phenoxy group, and a cyano group. The divalent organic group may contain a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a halogen atom in addition to a carbon atom and a hydrogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0192] The carbon number of the divalent organic group having 1 to 15 carbon atoms is preferably 1 to 14, and more preferably 1 to 10, from the viewpoints of obtaining a resin composition having better reactivity with compound (A) and having less voids, chip adhesiveness, and moisture absorption and heat resistance.

[0193] The alkylene group may be linear or branched. Examples of such alkylene groups include methylene, ethylene, ethylidene, propylene, trimethylene, isopropylidene, 2,2-dimethylpropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, undecylene, tridecylene, tetradecylene, pentadecylene, neopentylene, dimethylbutylene, methylhexylene, and the like. Examples of alkylene groups include alkylene groups such as ethylhexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyldodecylene, methylundecylene, methyltridecylene, methyltetradecylene, and methylpentadecylene. Among these, alkylene groups having 1 to 12 carbon atoms are preferred, alkylene groups having 1 to 6 carbon atoms are more preferred, and one or more selected from the group consisting of methylene, ethylene, and isopropylidene groups are even more preferred, with methylene being even more preferred, from the viewpoint of obtaining a resin composition having even better reactivity with compound (A) and even better low voids, chip adhesiveness, and moisture absorption and heat resistance.

[0194] The alkenylene group may be linear or branched. Examples of such alkenylene groups include vinylene, 1-methylvinylene, propenylene, isopropenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene, isopentylene, cyclopentenylene, cyclohexenylene, and dicyclopentadienylene.

[0195] Alkenylene groups may be linear or branched, and include, for example, ethynylene, propynylene, and butynylene groups.

[0196] Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a dicyclohexylene group, a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group.

[0197] Examples of the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, and a biphenyldiyl group.

[0198] The alkyl group having 1 to 6 carbon atoms may be linear or branched. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a neopentyl group, and an n-hexyl group. Among these, one or more selected from the group consisting of a methyl group, an ethyl group, and an n-propyl group are preferred, since they provide a resin composition with better reactivity with the compound (A) and with better low void properties, chip adhesiveness, and moisture absorption heat resistance.

[0199] Since it is possible to obtain a resin composition having even better reactivity with the compound (A) and even better low void properties, chip adhesiveness, and moisture absorption and heat resistance, R 1 are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and further preferably a hydrogen atom.

[0200] In order to obtain a resin composition having even better reactivity with compound (A) and even better low void properties, chip adhesiveness, and moisture absorption heat resistance, n is preferably an integer of 1 to 20, more preferably an integer of 2 to 15, and even more preferably an integer of 2 to 10.

[0201] The allylphenol compound (B1) preferably contains an allylphenol compound (B2) represented by the following formula (9), since this provides a resin composition having even better reactivity with the compound (A) and has even better low void properties, chip adhesiveness, and moisture absorption heat resistance.

[0202] [ka]

[0203] In formula (9), R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and n represents an integer of 1 or greater.

[0204] As for the alkyl group having 1 to 6 carbon atoms, the above may be referred to.

[0205] Since even more excellent reactivity with the compound (A) can be obtained and a resin composition having even more excellent low void properties, chip adhesiveness, and moisture absorption and heat resistance can be obtained, R 2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.

[0206] In order to obtain a resin composition having even better reactivity with compound (A) and even better low void properties, chip adhesiveness, and moisture absorption heat resistance, n is preferably an integer of 1 to 20, more preferably an integer of 2 to 15, and even more preferably an integer of 2 to 10.

[0207] The allylphenol compound (B) can be produced by a known method. For example, the allylphenol can be produced by reacting allylphenol with a crosslinking base. Examples of the crosslinking base include formaldehyde and acetaldehyde. Another example of the production method is to react a polyhydric hydroxy resin with an allyl halide, convert at least a part of the hydroxyl groups of the polyhydric hydroxy resin into an allyl ether, and then transfer the allyl groups in the allyl ether group by a Claisen transfer reaction. Examples of the polyhydric hydroxy resin include phenol novolac resin and bisphenol A novolac resin. Examples of the allyl halide include allyl chloride, allyl bromide, allyl fluoride, and allyl iodide. Specifically, the production method described in Japanese Patent No. 6319703 can be referred to.

[0208] Moreover, as the allylphenol compound (B), commercially available products may be used. Examples of commercially available products include the APG series (low viscosity allylphenol resins), the LVA series (low volatility allylphenol resins), the SBA series (high heat resistance, low dielectric property biphenylene resins), and the FATC series (low polarity polyfunctional allylphenol resins) manufactured by Gun-ei Chemical Industry Co., Ltd. Examples of the LVA series include LVA01EK (trade name, in formula (9), R 2 are all hydrogen atoms, and a mixture of allylphenol compounds with different n's, n=3 (average value), allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) is an example.

[0209] In order to obtain a resin composition having better reactivity with the compound (A) and having better low void properties, chip adhesiveness, and moisture absorption heat resistance, the functional group equivalent ratio between the compound (A) and the allylphenol compound (B) in the resin composition of this embodiment is preferably 1 to 4, more preferably 1.5 to 3.5, and even more preferably 2 to 3.

[0210] In this embodiment, the functional group equivalent ratio is the ratio of the sum of the maleimide group equivalent in the compound (A) contained in the resin composition and the citraconic imide group equivalent in the compound (A) to the allyl group equivalent in the allyl phenol compound (B) contained in the resin composition, and is calculated by the following formula (1). In this embodiment, it is also possible to use two or more of either the compound (A) or the allyl phenol compound (B), but in that case, the method of calculating the functional group equivalent ratio is to calculate the number of functional groups (i.e., the maleimide group equivalent, the citraconic imide group equivalent, and the allyl group equivalent) for each component in each of the compound (A) and the allyl phenol compound (B), and calculate the total maleimide group equivalent, the total citraconic imide group equivalent, and the total allyl group equivalent by summing up the values. The functional group equivalent ratio is the value obtained by dividing the sum of the total maleimide group equivalent and the total citraconic imide group equivalent by the total allyl group equivalent. The number of functional groups is the value obtained by dividing the number of parts by mass of a component by the functional group equivalent of that component.

[0211] Formula (1): Functional group equivalent ratio = ((equivalent weight of maleimide group of compound (A) + equivalent weight of citraconimide group of compound (A)) / equivalent weight of allyl group of allylphenol compound (B)) = ((mass parts of maleimide compound (AA) in resin composition / functional group equivalent of maleimide compound (AA)) + (mass parts of citraconic imide compound (AB) in resin composition / functional group equivalent of citraconic imide compound (AB))) / (mass parts of allylphenol compound (B) in resin composition / functional group equivalent of allylphenol compound (B))

[0212] In the resin composition of this embodiment, the content of the allylphenol compound (B) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total of the compounds (A) and (B), in order to obtain a resin composition having even better reactivity with the compound (A) and even better low void properties, chip adhesiveness, and moisture absorption heat resistance.

[0213] In the resin composition of this embodiment, the content of the allylphenol compound (B) is preferably 3 to 50 parts by mass, more preferably 7 to 45 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of obtaining a resin composition having even better reactivity with the compound (A) and having even better low void properties, chip adhesiveness, and moisture absorption heat resistance.

[0214] [Other thermosetting resins or compounds] The resin composition of this embodiment may contain other thermosetting resins or compounds (hereinafter, simply referred to as "other thermosetting resins") different from compound (A) and compound (B) as long as the effect of this embodiment is exhibited. Examples of such other thermosetting resins include cyanate ester compounds, benzoxazine compounds, epoxy compounds, phenolic compounds other than compound (B), aminotriazine novolac resins, polyphenylene ether compounds, alkenyl-substituted nadiimide compounds, oxetane resins, and compounds having a polymerizable unsaturated group. These other thermosetting resins may be used alone or in appropriate mixture of two or more.

[0215] In the resin composition of the present embodiment, the content of each of the other thermosetting resins is usually 0.1 to 50 parts by mass, preferably 0.5 to 30 parts by mass, and may be 1 to 20 parts by mass, relative to 100 parts by mass in total of the compound (A) and the compound (B).

[0216] [Inorganic filler (C)] The resin composition of the present embodiment contains an inorganic filler (C) because excellent flame resistance and thermal conductivity can be obtained, the thermal expansion coefficient and hygroscopicity can be reduced, and high hygroscopic heat resistance can be obtained. By using the inorganic filler (C), the flame resistance and thermal conductivity of the cured product formed using the resin composition of the present embodiment can be improved, and the thermal expansion coefficient and hygroscopicity can be reduced. Therefore, the resin composition can have high hygroscopic heat resistance. By using the resin composition of the present embodiment as an underfill material, the stress applied to the resin composition during reflow can be reduced, and volatility can also be reduced due to low hygroscopicity, so that very high insulation reliability can be ensured.

[0217] When the resin composition of this embodiment is used as an underfill material, the average particle diameter of the inorganic filler (C) is preferably 3 μm or less, more preferably 1 μm or less, and may be 0.5 μm or less in terms of narrowing the pitch of electrodes arranged on a chip and narrowing the gap between electrodes. The lower limit of the average particle diameter is, for example, 10 nm or more. In this embodiment, the "average particle diameter" of the inorganic filler (C) means the median diameter of the inorganic filler (C). Here, the median diameter means a particle diameter such that, when the particle size distribution of a powder is divided into two based on a certain particle diameter, the volume of the particles on the larger particle diameter side and the volume of the particles on the smaller particle diameter side each account for 50% of the total powder. The average particle diameter (median diameter) of the inorganic filler (C) is measured by a wet laser diffraction / scattering method.

[0218] Examples of the inorganic filler (C) include silica such as natural silica, fused silica, amorphous silica, and hollow silica; aluminum compounds such as boehmite, aluminum hydroxide, alumina, and aluminum nitride; magnesium compounds such as magnesium oxide and magnesium hydroxide; calcium compounds such as calcium carbonate and calcium sulfate; molybdenum compounds such as molybdenum oxide and zinc molybdate; boron nitride; barium sulfate; talc such as natural talc and calcined talc; mica; glass such as short fiber glass, spherical glass, and fine powder glass (e.g., E glass, T glass, and D glass). In addition, when it is desired to impart electrical conductivity or anisotropic electrical conductivity to the resin composition of the present embodiment, metal particles such as gold, silver, nickel, copper, tin alloy, and palladium may be used as the inorganic filler (C).

[0219] Among these, the inorganic filler (C) preferably contains one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide, because it provides better flame resistance and thermal conductivity, can further reduce the thermal expansion coefficient and moisture absorption, and further provides higher moisture absorption heat resistance. It is more preferable to contain one or more selected from the group consisting of silica, alumina, and boron nitride, and of these, silica is even more preferable.

[0220] These inorganic fillers (C) can be used alone or in suitable mixture of two or more.

[0221] The inorganic filler (C) may be surface-treated with a silane coupling agent. The silane coupling agent used for surface treatment of the inorganic filler (C) is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances. For example, vinyl silane-based silane coupling agents such as vinyl trimethoxy silane and γ-(meth)acryloxypropyl trimethoxy silane; phenyl amino silane-based silane coupling agents such as N-phenyl-3-aminopropyl trimethoxy silane; phenyl silane-based silane coupling agents such as trimethoxyphenyl silane; imidazole silane-based silane coupling agents can be mentioned. These silane coupling agents can be used alone or in appropriate mixture of two or more.

[0222] As the silane coupling agent, since it reacts well with the compound (A) and the allylphenol compound (B), and obtains further excellent flame resistance and thermal conductivity, can further reduce the thermal expansion coefficient and moisture absorption, and obtains further high moisture absorption heat resistance, it is preferable to use one or more selected from the group consisting of vinylsilane-based silane coupling agents, phenylaminosilane-based silane coupling agents, and phenylsilane-based silane coupling agents, and more preferably vinylsilane-based silane coupling agents. Among the vinylsilane-based silane coupling agents, γ-(meth)acryloxypropyltrimethoxysilane is more preferable.

[0223] Examples of silica or silica surface-treated with a silane coupling agent include SFP-120MC (trade name) and SFP-130MC (trade name) manufactured by Denka Co., Ltd.; and 3SM-CM4 (trade name), 5SM-CM2 (trade name), 0.3 μm SX-CM1 (trade name), 0.3 μm SX-EM1 (trade name), 0.3 μm SV-EM1 (trade name), SC1050-MLQ (trade name), SC2050-MNU (trade name), SC2050-MTX (trade name), 2.2 μm SC6103-SQ (trade name), SE2053-SQ (trade name), Y50SZ-AM1 (trade name), YA050C-MJE (trade name), YA050C-MJM (trade name), YA050C-MJF (trade name), and YA050C-MJA (trade name) manufactured by Admatechs Co., Ltd.

[0224] In the resin composition of the present embodiment, the content of the inorganic filler (C) is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, and even more preferably 30 to 200 parts by mass, relative to 100 parts by mass of the total of the compound (A) and the allylphenol compound (B), because better flame resistance and thermal conductivity can be obtained, the thermal expansion coefficient and moisture absorption can be further reduced, and even higher moisture absorption heat resistance can be obtained. The upper limit of the content of the inorganic filler (C) may be 100 parts by mass.

[0225] In the resin composition of the present embodiment, the content of the inorganic filler (C) is preferably 5 to 500 parts by mass, more preferably 15 to 300 parts by mass, and even more preferably 25 to 200 parts by mass, relative to 100 parts by mass of the resin solid content in the resin composition, because better flame resistance and thermal conductivity can be obtained, the thermal expansion coefficient and moisture absorption can be further reduced, and even higher moisture absorption heat resistance can be obtained. The upper limit of the content of the inorganic filler (C) may be 100 parts by mass.

[0226] [Flux activator (D)] The resin composition of this embodiment preferably further contains a flux activator (D) from the viewpoint of exhibiting flux activity in flip chip mounting. The flux activator (D) is not particularly limited as long as it is an organic compound having one or more acidic sites in the molecule. For example, the acidic site is preferably a phosphoric acid group, a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group, and in a semiconductor device using the resin composition of this embodiment as an underfill material, from the viewpoint of more effectively preventing migration and corrosion of metals such as solder and copper constituting the joint, a phenolic hydroxyl group or a carboxyl group is more preferable. The flux activator (D) can be used alone or in a suitable mixture of two or more types.

[0227] The flux activator (D) preferably has an acid dissociation constant pKa of 3.8 or more and 15.0 or less in terms of sufficient removal of the oxide film at the joint, and more preferably has an acid dissociation constant pKa of 4.0 or more and 14.0 or less in terms of the storage stability of the varnish and of achieving both the storage stability and flux activity of the laminate having a layer of the resin composition (underfill material with supporting substrate).

[0228] The weight-average molecular weight or molecular weight of the flux activator (D) is preferably 200 or more, more preferably 250 or more, from the viewpoint of preventing the flux activator (D) from volatilizing before the flux activity is exhibited in flip-chip mounting, i.e., preventing the flux activator (D) from volatilizing before the oxide film of the joint is removed. From the viewpoint of having mobility as a flux activator and obtaining sufficient flux activity, the weight-average molecular weight or molecular weight of the flux activator (D) is preferably 8000 or less, more preferably 4000 or less, even more preferably 1000 or less, and even more preferably 600 or less.

[0229] Examples of the flux activator (D) include rosin-based resins such as abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, palustric acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, hydrogenated rosin ester, and rosin-modified maleic acid resin; diamines such as N,N'-bis(salicylidene)-1,2-propanediamine and N,N'-bis(salicylidene)-1,3-propanediamine; and phenolphthalein. Among these, the flux activator (D) preferably contains a rosin-based resin. These flux activators (D) are preferred in terms of solubility in solvents, storage stability of the varnish, moisture absorption heat resistance, insulation reliability, and storage stability and flux activity of a laminate having a layer containing a resin composition.

[0230] Among these, from the viewpoint of preventing inactivation by the compound (A), the flux activator (D) is more preferably one or more selected from the group consisting of dehydroabietic acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, hydrogenated rosin ester, rosin modified maleic acid resin, N,N'-bis(salicylidene)-1,2-propanediamine, and N,N'-bis(salicylidene)-1,3-propanediamine. Moreover, since these flux activators have relatively low reactivity, they hardly react with the compounds (A) and (B), and therefore are more preferable in that sufficient flux activity required for removing oxide films is maintained. Furthermore, from the viewpoint of obtaining even more excellent flux activity, the flux activator (D) is even more preferably a hydrogenated rosin ester.

[0231] The flux activator (D) may be a commercially available product. Examples of rosin-based resins include KR-85 (trade name, the same below) of the Pine Crystal (registered trademark, the same below), KR-612, KR-614, KE-100, KE-311, PE-590, KE-359, KE-604, KR-120, KR-140, KR-614, D-6011, and KR-50M; Marquid No. 32 (all manufactured by Arakawa Chemical Industries Co., Ltd.).

[0232] In the resin composition of the present embodiment, the content of the flux activator (D) is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the total of the compound (A) and the compound (B), from the viewpoints of ensuring sufficient flux activity during flip-chip mounting, as well as solubility in a solvent, storage stability of the varnish, insulation reliability, and storage stability of a laminate having a layer containing the resin composition.

[0233] In the resin composition of the present embodiment, the content of the flux activator (D) is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 3 to 25 parts by mass, relative to 100 parts by mass of the resin solid content in the resin composition, from the viewpoints of ensuring sufficient flux activity during flip chip mounting, as well as solubility in a solvent, storage stability of the varnish, insulation reliability, and storage stability of a laminate having a layer containing the resin composition.

[0234] [Other ingredients] In the resin composition of the present embodiment, other components may be included as long as they do not impair the effects of the resin composition of the present embodiment. The other components may include one or more components other than the compound (A), the compound (B), other thermosetting resins or compounds, the inorganic filler (C), and the flux activator (D). The other components are not particularly limited, but may include, for example, a curing catalyst, a flexibility-imparting component, a silane coupling agent, a wetting and dispersing agent, and an additive. The other components may be used alone or in a suitable mixture of two or more.

[0235] (curing catalyst) The resin composition of this embodiment may contain a curing catalyst as long as it does not impair the effect of the resin composition of this embodiment. By containing a curing catalyst in the resin composition, the reaction rate between the compound (A) and the compound (B) and the polymerization rate of the compound (A) can be more suitably controlled, so that the curing rate of the resin composition can be suitably controlled, and a resin composition having suitable moldability tends to be obtained. The curing catalyst is not particularly limited as long as it is a compound that can promote the reaction between the compound (A) and the compound (B) and the polymerization reaction of the compound (A). The curing catalyst can be used alone or in a suitable mixture of two or more types.

[0236] Examples of the curing catalyst of the present embodiment include organic peroxides, imidazole compounds, azo compounds, and tertiary amines such as triethylamine and tributylamine, as well as derivatives thereof. Among these, the curing catalyst preferably contains one or more selected from the group consisting of organic peroxides and imidazole compounds, and more preferably contains both an organic peroxide and an imidazole compound, because the reaction rate, polymerization rate, and curing rate can be more suitably controlled.

[0237] In this embodiment, the content of the curing catalyst is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition, since this allows more suitable control of the reaction rate, polymerization rate, and curing rate.

[0238] ·Organic peroxide The organic peroxide according to the present embodiment is not particularly limited as long as it is a compound that releases an active substance (radical) that can promote the reaction between the compound and the compound (B) and the polymerization reaction of the compound (A) by heat, and any known organic peroxide can be used. The organic peroxide can be used alone or in a suitable mixture of two or more kinds.

[0239] In this embodiment, the 10-hour half-life temperature of the organic peroxide is preferably 100° C. or higher, and from the viewpoint of manufacturability, more preferably 110° C. or higher. Since the solvent removal step during production can be performed at a high temperature, it is preferable that the organic peroxide has a 10-hour half-life temperature in the above range.

[0240] Examples of organic peroxides include ketone peroxides such as dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, benzoyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide; peroxyketals of 1,1-di(t-butylperoxy)cyclohexane and 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane; tert-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; and di(2-t-butylperoxy)cyclohexane. peroxydicarbonates such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, α,α'-di(t-butylperoxy)diisopropylbenzene, and di-t-butyl peroxide; diacyl peroxides such as dibenzoyl peroxide and di(4-methylbenzoyl)peroxide; peroxydicarbonates such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate; and peroxy esters such as 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-hexyl peroxybenzoate, t-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexanoate. Since the reaction rate, polymerization rate, and curing rate can be more suitably controlled, one or more selected from the group consisting of dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, α,α'-di(t-butylperoxy)diisopropylbenzene, and tert-butyl hydroperoxide are preferred.

[0241] In the resin composition of this embodiment, the content of the organic peroxide is preferably 0.01 to 10 parts by mass per 100 parts by mass of the resin solid content in the resin composition, since this makes it possible to more appropriately control the reaction rate, polymerization rate, and curing rate.

[0242] Imidazole compounds The imidazole compound is not particularly limited as long as it can promote the reaction between compound (A) and compound (B) and the polymerization reaction of compound (A), and any known imidazole compound can be used. The imidazole compound can be used alone or in a suitable mixture of two or more kinds.

[0243] Examples of the imidazole compound include 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 2,4,5-triphenylimidazole. Among these, 2-ethyl-4-methylimidazole is preferred because it can more suitably control the reaction rate, polymerization rate, and curing rate.

[0244] In the resin composition of this embodiment, the content of the imidazole compound is preferably 0.01 parts by mass to 10 parts by mass per 100 parts by mass of the resin solid content in the resin composition, since this allows for more optimal control of the reaction rate, polymerization rate, and curing rate.

[0245] ·Azo compounds The azo compound is not particularly limited as long as it can promote the reaction between compound (A) and compound (B) and the polymerization reaction of compound (A), and any known azo compound can be used. The azo compound can be used alone or in a suitable mixture of two or more kinds. Examples of azo compounds include 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile).

[0246] In the resin composition of the present embodiment, the content of the azo compound is preferably 0.01 to 10 parts by mass per 100 parts by mass of the resin solid content in the resin composition, since this allows more suitable control of the reaction rate, polymerization rate, and curing rate.

[0247] (Flexibility imparting component) The resin composition of the present embodiment may contain a flexibility-imparting component as long as it does not impair the effect of the resin composition of the present embodiment. The flexibility-imparting component is not particularly limited as long as it is a component that can impart flexibility to a layer containing the resin composition. Examples of such components include thermoplastic polymer compounds such as polyimide, polyamideimide, polystyrene, polyolefin, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), (meth)acrylonitrile butadiene rubber (NBR), polyurethane, polypropylene, (meth)acrylic oligomer, (meth)acrylic polymer, and silicone resin, other than the compound (A), compound (B), other thermosetting resin or compound, inorganic filler (C), flux activator (D), and curing catalyst. These flexibility-imparting components can be used alone or in appropriate mixture of two or more types.

[0248] In the resin composition of this embodiment, the content of the flexibility-imparting component is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin solid content in the resin composition, since this can improve the toughness and stress relaxation performance of the resin composition.

[0249] (Silane coupling agent) The resin composition of this embodiment may contain a silane coupling agent for the purpose of further improving the adhesion at the interface between the resin components such as the compound (A) and the compound (B) and the inorganic filler (C) and the moisture absorption heat resistance, as long as the effect of the resin composition of this embodiment is not hindered. Examples of the silane coupling agent include vinyl silane-based silane coupling agents such as vinyl trimethoxy silane and γ-(meth)acryloxypropyl trimethoxy silane; phenyl amino silane-based silane coupling agents such as N-phenyl-3-aminopropyl trimethoxy silane; phenyl silane-based silane coupling agents such as trimethoxyphenyl silane; and imidazole silane-based silane coupling agents. These silane coupling agents can be used alone or in appropriate mixture of two or more.

[0250] When a silane coupling agent is used, the content thereof is preferably 0.01 to 20 parts by mass per 100 parts by mass of the resin solid content in the resin composition, since this further improves the moisture absorption and heat resistance and further reduces the amount of volatilization during flip chip mounting, post-cure, and reflow.

[0251] (Wetting and dispersing agent) The resin composition of this embodiment may contain a wetting dispersant for the purpose of further improving the manufacturability of the laminate and further improving the dispersibility of the inorganic filler, as long as the effect of the resin composition of this embodiment is not impaired. The wetting dispersant is not particularly limited as long as it is a wetting dispersant generally used in paints and the like. For example, DISPERBYK (registered trademark)-110 (trade name), -111 (trade name), -180 (trade name), -161 (trade name), BYK-W996 (trade name), -W9010 (trade name), and -W903 (trade name) manufactured by BYK-Chemie Japan Co., Ltd. can be mentioned. These wetting dispersants can be used alone or in a suitable mixture of two or more kinds.

[0252] When a wetting dispersant is used, the content is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of further improving the manufacturability of the laminate. When two or more types of wetting dispersants are used in combination, it is preferable that the total amount of these satisfies the above ratio.

[0253] (Additives) The resin composition of the present embodiment may contain various additives for various purposes, so long as they do not impair the effects of the resin composition of the present embodiment. Examples of additives include compounds (A), (B), other thermosetting resins or compounds, inorganic fillers (C), flux activators (D), curing catalysts, flexibility-imparting components, silane coupling agents, and components other than wetting and dispersing agents. Examples of such components include ultraviolet absorbers, antioxidants, dyes, pigments, thickeners, lubricants, defoamers, leveling agents, gloss agents, flame retardants, and ion trapping agents. These additives may be used alone or in appropriate mixtures of two or more.

[0254] In the resin composition of the present embodiment, the content of each of the other additives is usually 0.01 to 10 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0255] [Method for producing resin composition] The resin composition of the present embodiment is not particularly limited in the manufacturing method as long as the resin composition having the above-mentioned composition can be obtained. The resin composition can be prepared, for example, by appropriately mixing the compound (A), the compound (B), other thermosetting resins or compounds, the inorganic filler (C), and, if necessary, the flux activator (D), and other components. If necessary, these components may be dissolved or dispersed in an organic solvent to form a varnish. The varnish can be suitably used when preparing a laminate. For a specific manufacturing method, the manufacturing method of the laminate and the examples described later may be referred to.

[0256] The organic solvent is not particularly limited as long as it can suitably dissolve or disperse each component in the resin composition of the present embodiment and does not impair the effect of the resin composition of the present embodiment. Examples of the organic solvent include alcohols such as methanol, ethanol, and propanol; ketones such as acetone, methyl ethyl ketone (hereinafter sometimes abbreviated as "MEK"), and methyl isobutyl ketone; amides such as dimethylacetamide and dimethylformamide; and aromatic hydrocarbons such as toluene and xylene. These organic solvents can be used alone or in appropriate mixtures of two or more.

[0257] [Resin sheet] The resin sheet contains the resin composition of this embodiment. Specifically, the resin sheet has a supporting substrate and a resin layer disposed on one or both sides of the supporting substrate, and the resin layer contains the resin composition of this embodiment. This resin sheet is also called a laminated resin sheet. The resin layer of the resin sheet is preferably a resin composition in an uncured state (A stage) that is applied to a supporting substrate and then semi-cured (B stage). As a manufacturing method for such a resin sheet, a method of manufacturing a composite of a B-stage resin layer and a supporting substrate is generally preferred. Specifically, a method of manufacturing a resin sheet by applying a resin composition in an uncured state (A stage) to a supporting substrate such as copper foil in the form of a varnish using a known method such as a bar coater, and then semi-curing (B stage) by a method of heating in a dryer at 60 to 200 ° C. for 1 to 60 minutes, etc., can be mentioned. In this embodiment, the uncured state (A stage) refers to a state in which the resin composition is almost not cured and is not gelled. The resin composition before being applied to the supporting substrate of the resin sheet is, for example, in the form of a mixture of the components of the resin composition (which may or may not contain a solvent) or a varnish in which the mixture is dissolved or dispersed in a solvent, and is in an uncured state (A stage).

[0258] Examples of the supporting substrate include organic films such as polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and polyimide film; release films obtained by applying a release agent to the surface of these films; conductor foils such as copper foil and aluminum foil; and plate-shaped materials such as glass plates, SUS plates, and FRP.

[0259] Examples of the application method include a method in which a solution obtained by dissolving the resin composition in a solvent is applied onto a supporting substrate using a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

[0260] Among the resin sheets, the single-layer resin sheet is obtained by forming a resin composition into a sheet. The manufacturing method of the single-layer resin sheet can be performed according to a conventional method, and is not particularly limited. For example, in the manufacturing method of the resin sheet, a method in which a solution in which the resin composition is dissolved in a solvent is applied onto a support substrate and dried, and then the support substrate is peeled off or etched from the resin sheet can be mentioned. In addition, a single-layer resin sheet can also be obtained without using a support substrate by supplying a solution in which the resin composition is dissolved in a solvent into a mold having a sheet-shaped cavity and drying it to form it into a sheet.

[0261] In producing a resin sheet or a single-layer resin sheet, the drying conditions for removing the solvent are preferably a temperature of 60 to 200°C for 1 to 60 minutes, since a low temperature makes the solvent likely to remain in the resin composition, and a high temperature causes the curing of the resin composition to proceed.

[0262] The thickness of the resin sheet or the resin layer of the single-layer resin sheet can be adjusted by the concentration of the resin composition solution and the coating thickness, and is not particularly limited. Generally, however, a thicker coating thickness makes it easier for the solvent to remain when dried, so that a thickness of 0.1 to 500 μm is preferable.

[0263] The resin sheet or single-layer resin sheet can be used, for example, as a material for forming wiring circuits on semiconductor wafers and semiconductor chip mounting substrates.

[0264] [Laminate] By applying the resin composition of the present embodiment onto a supporting substrate, a laminate having a layer containing the resin composition, which has low voids, chip adhesiveness, and excellent moisture absorption and heat resistance, can be obtained. The laminate of the present embodiment includes a supporting substrate and a layer containing the resin composition of the present embodiment laminated on the supporting substrate. Such a laminate is obtained by attaching the resin composition of the present embodiment to the supporting substrate. The supporting substrate is not particularly limited, but a polymer film can be used. Examples of the material of the polymer film include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polybutene, polybutadiene, ethylene-propylene copolymer, polymethylpentene, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polyurethane resins; polyimide resins; polyamide resins, etc. Examples of the supporting substrate include films containing these resins, etc., and release films in which a release agent is applied to the surface of these films. Among these, films containing one or more resins selected from the group consisting of polyester-based resins, polyimide-based resins, and polyamide-based resins, and release films obtained by applying a release agent to the surface of these films are preferred, and films containing polyethylene terephthalate, a type of polyester-based resin, or release films obtained by applying a release agent to the surface of a film containing polyethylene terephthalate are more preferred.

[0265] The thickness of the support substrate is preferably 10 to 100 μm in terms of easier production of the laminate, for example, better stability of the coating thickness when the resin composition is applied to the support substrate and better transportability of the laminate. The lower limit of the thickness of the support substrate is more preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 25 μm or more in terms of better yield when producing the laminate. The upper limit of the thickness of the support substrate is more preferably 80 μm or less, and even more preferably 50 μm or less in terms of the fact that the support substrate is not ultimately present as a component of the semiconductor device and is peeled off during the process, and in terms of the production cost of the laminate.

[0266] There is no particular limitation on the method for producing the laminate of the present embodiment by forming a layer (resin composition layer) containing the resin composition of the present embodiment on a supporting substrate. For example, a method of applying a varnish in which the resin composition of the present embodiment is dissolved or dispersed in an organic solvent to the surface of the supporting substrate, and drying the varnish under heating and / or reduced pressure to remove the solvent and solidify the resin composition of the present embodiment to form a resin composition layer. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content ratio of the organic solvent relative to the total mass (100 parts by mass) of the resin composition layer is usually 10 parts by mass or less, preferably 5 parts by mass or less. The conditions for achieving such drying also vary depending on the type and amount of the organic solvent in the varnish. For example, in the case of a varnish containing 10 to 200 parts by mass of methyl ethyl ketone relative to 100 parts by mass of the resin solid content in the resin composition, drying for 1 to 60 minutes under heating conditions of 60 to 160°C under 0.5 to 2 atm is usually a guideline. The thickness of the resin composition layer in the laminate of this embodiment is preferably in the range of 5 to 500 μm, more preferably in the range of 10 to 100 μm, from the viewpoint of more effectively removing volatile components with relatively low molecular weights when the resin composition layer is dried and more effectively and reliably exhibiting the function of the laminate. After the laminate of this embodiment is produced, for the purpose of storage or the like, a protective film may be laminated separately on the surface of the laminate opposite to the surface on which the supporting substrate is located.

[0267] [Semiconductor chip with resin composition layer, and semiconductor chip mounting substrate with resin composition layer] The semiconductor chip with a resin composition layer of the present embodiment includes a semiconductor chip and a layer containing the resin composition of the present embodiment laminated on the semiconductor chip. Also, the substrate for mounting a semiconductor chip with a resin composition layer of the present embodiment includes a substrate for mounting a semiconductor chip and a layer containing the resin composition of the present embodiment laminated on the substrate for mounting a semiconductor chip.

[0268] A method for producing a semiconductor chip with a resin composition layer of this embodiment can be obtained, for example, by laminating the laminate of this embodiment so that the resin composition layer faces the surface of a semiconductor wafer on which electrodes are formed, i.e., the surface on which bonding with a substrate is performed, peeling off the support base material in the laminate, and then performing individual division with a dicing saw or the like. A method for producing a semiconductor chip mounting substrate with a resin composition layer of this embodiment can be obtained, for example, by laminating the laminate of this embodiment so that the resin composition layer faces the surface of a semiconductor chip mounting substrate on which chips are mounted, and peeling off the support base material in the laminate.

[0269] The method of laminating the laminate of this embodiment to a semiconductor wafer or a substrate for mounting semiconductor chips is not particularly limited, but a vacuum pressure laminator can be suitably used. In this case, a method of laminating the laminate of this embodiment by applying pressure via an elastic body such as rubber is preferred. The lamination conditions are, for example, a temperature of 50 to 140°C and a pressure of 1 to 11 kgf / cm, which are generally used in the industry. 2 The lamination process is carried out under a contact pressure in the range of 1000 to 2000 mmHg and a reduced atmospheric pressure of 20 hPa or less. After the lamination process, the laminated body may be smoothed by hot pressing with a metal plate. The lamination process and the smoothing process can be carried out continuously by a commercially available vacuum pressure laminator. In either case, the support substrate is removed from the laminate attached to the semiconductor wafer or the semiconductor chip mounting substrate before the chip is flip-chip mounted.

[0270] [Semiconductor Devices] The semiconductor device of this embodiment includes a semiconductor chip with a resin composition layer of this embodiment and / or a substrate for mounting a semiconductor chip with a resin composition layer of this embodiment. The semiconductor device of this embodiment includes a semiconductor chip with a resin composition layer of this embodiment. The semiconductor device of this embodiment includes a substrate for mounting a semiconductor chip with a resin composition layer of this embodiment. The semiconductor device of this embodiment includes a semiconductor chip with a resin composition layer of this embodiment, and a substrate for mounting a semiconductor chip with a resin composition layer of this embodiment.

[0271] The method for manufacturing the semiconductor device of this embodiment includes, for example, a method of mounting the semiconductor chip with the resin composition layer of this embodiment on a semiconductor chip mounting substrate. A semiconductor chip may be mounted on the semiconductor chip mounting substrate with the resin composition layer of this embodiment. In the method for mounting the semiconductor chip with the resin composition layer on the semiconductor chip mounting substrate and the method for mounting the semiconductor chip on the semiconductor chip mounting substrate with the resin composition layer, a flip chip bonder compatible with a thermocompression bonding method can be suitably used. In this embodiment, the case where the semiconductor chip is flip-chip mounted on the semiconductor chip mounting substrate is explained for convenience, but the object to which the resin composition of this embodiment is applied while flip-chip mounting the semiconductor chip can be other than the semiconductor chip mounting substrate. For example, the resin composition of this embodiment can be used for the joint between the semiconductor wafer and the semiconductor chip when mounting the semiconductor chip on the semiconductor wafer, or the joint between each semiconductor chip of a chip stack that connects the semiconductor chips via TSV (Through Silicon Via) or the like, and the effect of this embodiment can be obtained in either case. By flip chip mounting, the chip, the resin composition as an underfill material, and the substrate are bonded to each other, and a semiconductor device is obtained. Flip chip mounting is performed, for example, at a heating temperature of 220° C. or higher, preferably in the range of 240 to 300° C., and the heating time is not particularly limited, but is usually in the range of 1 to 20 seconds. According to the resin composition of the present embodiment, the generation of voids after flip chip mounting can be suitably suppressed.

[0272] The underfill material in the semiconductor device is cured by heating in the post-cure process performed after flip-chip mounting. In the post-cure process, a curing process in which the underfill material is cured by applying temperature using a dryer or the like, or a pressurized curing process in which the underfill material is cured by applying temperature and pressure, can be used. In order to efficiently remove voids originating from the underfill material generated during mounting, it is preferable to use the pressurized curing process. In the pressurized curing process, the underfill material can be melted and flowed by applying temperature and pressure, so that the underfill material can be refilled into the voids. Since the resin composition of this embodiment has a suitable viscosity even at the heating temperature in the pressurized curing process, even if voids are generated, the resin composition is refilled so as to completely fill the voids. Therefore, the voids can be efficiently removed. In addition, the pressurized curing process is performed, for example, at a heating temperature of 120° C. or more, preferably in the range of 180 to 220° C., at a pressure of 0.1 MPa or more, preferably in the range of 0.2 to 1.0 MPa, and the heating time is not particularly limited, but is usually performed in the range of 0.5 to 4 hours. In order to control the melt viscosity of the underfill material and efficiently remove voids, the heating temperature may be in two or more stages. For example, the first stage may be a treatment at 140°C for 0.2 to 2 hours, followed by a treatment at 200°C for 2 hours.

[0273] After the semiconductor device is manufactured, a motherboard or the like is usually further joined to the semiconductor device via solder balls or the like. This process usually includes a reflow process for melting the solder balls. The reflow process is carried out in a reflow furnace, and is typically carried out at a high temperature of 240° C. or higher, preferably 250 to 300° C., to melt the solder balls, for example, with a heating time that is not particularly limited but is usually within a range of 30 seconds to 30 minutes. EXAMPLES

[0274] The present embodiment will be described in more detail below using examples and comparative examples, but the present embodiment is not limited to the following examples.

[0275] [Preparation of resin composition and laminate] Example 1 35 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A) and 35 parts by mass of a maleimide compound represented by formula (5) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., maleimide group (functional group) equivalent: 275 g / eq, weight average molecular weight: 105 50 parts by mass of a MEK (methyl ethyl ketone) solution (non-volatile content 70%) of 100 parts by mass (35 parts by mass calculated as non-volatile content), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and an allylphenol compound (LVA01EK (trade name), in formula (9), R 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass in terms of non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.3. This varnish was applied to a 38 μm-thick polyethylene terephthalate film (TR1-38 (product name, supporting substrate), Unitika Ltd.) whose surface was coated with a release agent, and then heated and dried at 100°C for 5 minutes under 1 atmosphere to obtain a laminate having a B-staged resin composition layer of 35 μm in thickness.

[0276] Example 2 23 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A), 47.1 parts by mass (33 parts by mass in terms of nonvolatile content) of an MEK solution (70% nonvolatile content) of a maleimide compound represented by formula (5) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., maleimide group (functional group) equivalent: 275 g / eq, weight average molecular weight: 1050) as compound (A), and As compound (A), 14 parts by mass of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Kasei Kogyo Co., Ltd., maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500), as compound (A), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Kasei Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and an allylphenol compound (LVA01EK (trade name), in formula (9), R 2are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.4. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0277] Example 3 37 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A), 1.4 parts by mass (1 part by mass calculated as nonvolatile content) of an MEK solution (70% nonvolatile content) of a maleimide compound represented by formula (5) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., maleimide group (functional group) equivalent: 275 g / eq, weight average molecular weight: 1050) as compound (A), and As compound (A), 32 parts by mass of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500), as compound (A), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and an allylphenol compound (LVA01EK (trade name), in formula (9), R 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 3.0. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0278] Example 4 25.5 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A), 0.7 parts by mass (0.5 parts by mass in terms of nonvolatile content) of an MEK solution (70% nonvolatile content) of a maleimide compound represented by formula (5) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., maleimide group (functional group) equivalent: 275 g / eq, weight average molecular weight: 1050) as compound (A), and As compound (A), 44 parts by mass of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Kasei Kogyo Co., Ltd., maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500) and as compound (A), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Kasei Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) and as compound (B), an allylphenol compound (LVA01EK (trade name), in which R 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.8. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0279] Example 5 28 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A), 14 parts by mass of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500) as compound (A), and 2,2'-bis(4-(4-maleimidophenyl)methane as compound (A) were used. 28 parts by mass of (1-phenyl-2-phenyl-1,3-di ... 2are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.4. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0280] Example 6 21 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A), 21 parts by mass of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500) as compound (A), and 2,2'-bis(4-(4-maleimidophenyl)methane as compound (A) were used. 28 parts by mass of (1-phenyl-2-phenyl-1,3-di ... 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.5. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0281] Example 7 17.5 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A), 17.5 parts by mass of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500) as compound (A), and 2,2'-bis(4-(4-maleimidophenyl)methane as compound (A) were used. 35 parts by mass of imidophenoxy)phenyl)propane (BMI-80 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 285 g / eq, molecular weight: 570.6), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and an allylphenol compound (LVA01EK (trade name), in formula (9), R 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.4. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0282] Example 8 17 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A), 31 parts by mass of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500) as compound (A), and 2,2'-bis(4-(4-maleimidophenyl)methane as compound (A) were used. 22 parts by mass of (1-phenyl-2-phenyl-2-phenyl-1,3-di ... 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.6. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0283] Example 9 70 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and an allylphenol compound (LVA01EK (trade name), Gun-ei Chemical Industry Co., Ltd., in formula (9), R 2 are all hydrogen atoms, n is a mixture of allylphenol compounds with different n, n = 3 (average value), allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60 mass%, average particle size: 300 nm) as inorganic filler (C) in MEK solution 83.3 parts by mass (50 parts by mass calculated as non-volatile content) of the ester (60% non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of the compound (A) to the allylphenol compound (B) was 2.6. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0284] Example 10 As compound (A), 35 parts by mass of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500), 35 parts by mass of 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane (BMI-80 (trade name), K.I. Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 285 g / eq, molecular weight: 570.6) as compound (A), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and an allylphenol compound (LVA01EK (trade name), in formula (9), R 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.5. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0285] Comparative Example 1 As compound (A), 70 parts by mass of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Kasei Kogyo Co., Ltd., maleimide group (functional group) equivalent: 186 g / eq, weight average molecular weight: 500), as compound (A), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Kasei Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and an allylphenol compound (LVA01EK (trade name), in formula (9), R 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 3.0. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0286] Comparative Example 2 100 parts by mass (70 parts by mass calculated as non-volatile content) of an MEK solution (70% non-volatile content) of a maleimide compound represented by formula (5) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., maleimide group (functional group) equivalent: 275 g / eq, weight average molecular weight: 1050) as compound (A), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Chemical Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and an allylphenol compound (LVA01EK (trade name), in formula (9), R 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.1. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0287] Comparative Example 3 50 parts by mass (35 parts by mass in terms of non-volatile content) of an MEK solution (non-volatile content 70%) of a maleimide compound represented by formula (5) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., maleimide group (functional group) equivalent: 275 g / eq, weight average molecular weight: 1050) as compound (A) and 50 parts by mass (35 parts by mass in terms of non-volatile content) of a maleimide compound represented by formula (6) (BMI-2300 (trade name), Daiwa Kasei Kogyo Co., Ltd., maleimide group (functional group) equivalent: 275 g / eq, weight average molecular weight: 1050) as compound (A) were mixed. 35 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and 10 parts by mass of an allylphenol compound (LVA01EK (trade name), in formula (9), R 2 are all hydrogen atoms, and n is a mixture of allylphenol compounds with different n, n = 3 (average value, Gun-ei Chemical Industry Co., Ltd., allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). 83.3 parts by mass of MEK solution (60% non-volatile content) (50 parts by mass calculated as non-volatile content) and 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid content concentration of 60% by mass. The functional group equivalent ratio of compound (A) to allylphenol compound (B) was 2.5. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0288] Comparative Example 4 35 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A) and 35 parts by mass of a maleimide compound represented by formula (5) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., maleimide group (functional group) equivalent: 275 g / eq, weight average molecular weight: 1 50 parts by mass of an MEK solution (non-volatile content 70%) of 0.50050 (35 parts by mass in terms of non-volatile content), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and 10 parts by mass of a phenol novolac resin (Phenolite (registered trademark) TD-2090-60M (trade name), DIC Corporation, weight average molecular weight: 3700) 33.3 parts by mass (20 parts by mass in terms of non-volatile content) of an MEK solution (non-volatile content 60% by mass) of an inorganic filler (C) (average molecular weight: 8,500, nitrogen content: 0% by mass, hydroxyl group (functional group) equivalent: 105 g / eq.) and 83.3 parts by mass of an MEK solution (non-volatile content 60%) of slurry silica (3SM-CM4 (trade name), Admatechs Co., Ltd., methacrylsilane surface-treated silica, solid content 60% by mass, average particle size: 300 nm) as inorganic filler (C). parts by mass (50 parts by mass calculated as non-volatile content) of this solution were mixed with 10 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (product name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) as a flux activator (D), MEK was added so that the solid concentration was 60% by mass, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70°C to obtain a varnish with a solid concentration of 60% by mass. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0289] Comparative Example 5 35 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I. Chemicals Co., Ltd., maleimide group (functional group) equivalent: 221 g / eq, molecular weight: 550) as compound (A) and 35 parts by mass of a maleimide compound represented by formula (5) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., maleimide group (functional group) equivalent: 275 g / eq, weight average molecular weight: 105 50 parts by mass of an MEK solution (non-volatile content 70%) of 100 parts by mass (35 parts by mass calculated as non-volatile content), 10 parts by mass of a maleimide compound represented by formula (3) (BMI-1000P (trade name), K.I. Chemical Industry Co., Ltd., maleimide group (functional group) equivalent: 702 g / eq, weight average molecular weight: 3700) as compound (A), and an allylphenol compound (LVA01EK (trade name), Gun-ei Chemical Industry Co., Ltd., in formula (9), R 2 are all hydrogen atoms, and a mixture of allylphenol compounds with different n, n = 3 (average value), allyl group (functional group) equivalent: 154 g / eq, weight average molecular weight: 1000) in MEK solution (non-volatile content 85%) 23.5 parts by mass (20 parts by mass in terms of non-volatile content) and hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) 10 parts by mass as a flux activator (D) were mixed, MEK was added so that the solid content concentration was 60 mass%, and the mixture was stirred for 40 minutes using a high-speed stirrer in a water bath at 70 ° C. to obtain a varnish with a solid content concentration of 60 mass%. The functional group equivalent ratio between the compound (A) and the allylphenol compound (B) was 2.3. Using this varnish, a laminate was obtained in the same manner as in Example 1, in which the B-staged resin composition layer had a thickness of 35 μm.

[0290] [Measurement and Evaluation] The following measurements and evaluations were carried out using the laminates obtained in Examples 1 to 10 and Comparative Examples 1 to 5. The results are shown in Tables 1 and 2.

[0291] (1) Measurement of minimum melt viscosity A predetermined number of laminates 1 each having a resin composition layer thickness of 35 μm obtained in Examples 1 to 10 and Comparative Examples 1 to 5 were prepared. First, two sheets of the laminate 1 were prepared, and arranged so that the resin composition layers of the laminate 1 were in contact with each other, and laminated using a diaphragm type vacuum laminator (V-130 (trade name), manufactured by Nikko Materials Co., Ltd.) under the conditions of a vacuum drawing time of 30 seconds, a temperature of 60°C, a pressure of 0.5 MPa, and a pressurization time of 60 seconds. The polyethylene terephthalate film on one side of the obtained laminate 2 was peeled off. Thereafter, the resin composition layer on the peeled surface of the laminate 2 was placed so as to be in contact with the resin composition layer of another laminate 3 obtained in the same Example or Comparative Example, and laminated under the above conditions. This operation was repeated until the thickness of the resin composition layer became 0.4 to 0.6 mm, and a laminate 4 having polyethylene terephthalate films laminated on both sides was obtained. The obtained laminate 4 having a resin composition layer thickness of 0.4 to 0.6 mm was cut into a square of 10 mm x 10 mm, and the polyethylene terephthalate films on both sides of the cut laminate 4 were peeled off. The resin composition layer obtained was used to measure the minimum melt viscosity with a rheometer (HAAKE MARS60 (trade name), manufactured by Thermo Fisher Scientific). As a heating device attached to the rheometer, an electric heater type temperature control module (HAAKE MARS TM-EL-H (trade name) and Electrical Temperature Module TM-EL-P (trade name)) was used. As an adapter, a ceramic shaft for disposable plates AdapterP3 (trade name) was used to which an aluminum disposable upper parallel plate D / PB Al (trade name, plate diameter: 8.0 mm) was attached, and this adapter was attached to a rheometer HAAKE MARS60 (trade name). As a measurement table, an aluminum disposable lower parallel plate TMP25 Al (trade name, 25.0 mm) was used, and this measurement table was attached to an electric heater type temperature control module Electrical Temperature Module TM-EL-P (trade name).Then, in a rheometer, the resin composition layer obtained above, 10 mm x 10 mm x 0.4 to 0.6 mmt, was placed on the measurement table, and the adaptor (upper parallel plate) was lowered until it contacted the placed resin composition layer, and the resin composition layer was adhered to the upper and lower disposable parallel plates while maintaining the measurement temperature of 40 ° C, the pressure of 2 N, and the measurement time of 1 minute. Then, the melt viscosity was measured in the range of 40 ° C to 260 ° C under the conditions of a measurement start temperature of 40 ° C, a heating rate of 10 ° C / min, a frequency of 10.0 rad / sec, and a strain of 0.1%, and the viscosity at which the viscosity was the lowest in that temperature range was taken as the minimum melt viscosity (unit: Pa · s) of the resin composition. Note that during the measurement, the gap (gap) between the upper parallel plate and the lower parallel plate was constant. Also, a rheometer chart measured using the resin composition layer prepared using the laminate obtained in Example 1 is shown in Figure 1. As shown in FIG. 1, the lowest viscosity, that is, the minimum melt viscosity of the resin composition, was 22 (Pa·s).

[0292] (2) Viscosity measurement at 200℃ A predetermined number of laminates 1 each having a resin composition layer thickness of 35 μm obtained in Examples 1 to 10 and Comparative Examples 1 to 5 were prepared. First, two sheets of the laminate 1 were prepared, and arranged so that the resin composition layers of the laminate 1 were in contact with each other, and laminated using a diaphragm type vacuum laminator (V-130 (trade name), manufactured by Nikko Materials Co., Ltd.) under the conditions of a vacuum drawing time of 30 seconds, a temperature of 60°C, a pressure of 0.5 MPa, and a pressurization time of 60 seconds. The polyethylene terephthalate film on one side of the obtained laminate 2 was peeled off. Thereafter, the resin composition layer on the peeled surface of the laminate 2 was placed so as to be in contact with the resin composition layer of another laminate 3 obtained in the same Example or Comparative Example, and laminated under the above conditions. This operation was repeated until the thickness of the resin composition layer became 0.4 to 0.6 mm, and a laminate 4 having polyethylene terephthalate films laminated on both sides was obtained. The obtained laminate 4 having a resin composition layer thickness of 0.4 to 0.6 mm was cut into a square of 10 mm x 10 mm, and the polyethylene terephthalate films on both sides of the cut laminate 4 were peeled off. The obtained resin composition layer was used to measure the viscosity at 200°C using a rheometer (HAAKE MARS60 (trade name), manufactured by Thermo Fisher Scientific). As a heating device attached to the rheometer, an electric heater type temperature control module (HAAKE MARS TM-EL-H (trade name) and Electrical Temperature Module TM-EL-P (trade name)) was used. As an adapter, a ceramic shaft for disposable plates AdapterP3 (trade name) was used to which an aluminum disposable upper parallel plate D / PB Al (trade name, plate diameter: 8.0 mm) was attached, and this adapter was attached to a rheometer HAAKE MARS60 (trade name). As a measurement table, an aluminum disposable lower parallel plate TMP25 Al (trade name, 25.0 mm) was used, and this measurement table was attached to an electric heater type temperature control module Electrical Temperature Module TM-EL-P (trade name).Then, in a rheometer, the resin composition layer obtained above, 10 mm x 10 mm x 0.4 to 0.6 mmt, was placed on the measurement table, and the adapter (upper parallel plate) was lowered until it contacted the placed resin composition layer, and the resin composition layer was adhered to the upper and lower disposable parallel plates while maintaining the measurement temperature of 40 ° C, the pressure of 2 N, and the measurement time of 1 minute. Then, the viscosity at 200 ° C was measured under the conditions of a measurement start temperature of 40 ° C, a heating rate of 10 ° C / min, a frequency of 10.0 rad / sec, and a strain of 0.1%, and the value at that time was taken as the viscosity of the resin composition (unit: Pa · s). Note that during the measurement, the gap (gap) between the upper parallel plate and the lower parallel plate was constant. Also, a chart of the rheometer measured using the resin composition layer prepared using the laminate obtained in Example 1 is shown in Figure 1. As shown in Figure 1, the viscosity at 200 ° C was 23 (Pa · s).

[0293] (3) Evaluation of voids after flip chip mounting The laminates obtained in Examples 1 to 10 and Comparative Examples 1 to 5, each having a resin composition layer thickness of 35 μm, were cut into 8 mm×8 mm squares. Then, the laminates were arranged so that the resin composition layer of the cut laminate was in contact with the 15 μm copper circuit surface of the pad portion of the semiconductor chip mounting substrate (WALTS-KIT CC80(W)-0105JY (trade name) manufactured by Waltz Corporation), and laminated using a diaphragm-type vacuum laminator (V-130 (trade name), manufactured by Nikko Materials Co., Ltd.) under the conditions of a vacuum drawing time of 30 seconds, a temperature of 60° C., a pressure of 0.5 MPa, and a pressurization time of 60 seconds. Then, the polyethylene terephthalate film in the laminate in which the semiconductor chip mounting substrate and the resin composition layer were laminated was peeled off. Next, using a flip chip bonder (LFB-2301 (trade name), Shinkawa Co., Ltd.), a laminate in which a semiconductor chip mounting substrate and a resin composition layer are laminated is placed on a semiconductor chip having a Cu pillar composed of copper and solder as an electrode under conditions of a stage temperature of 85 ° C., a bond head temperature of 120 ° C., a load of 30 N, and a time of 1 second, so that the peeled surface of the resin composition layer is in contact with the semiconductor chip, and then the laminate is thermocompressed under conditions of a bond head temperature of 260 ° C., a load of 30 N, and a time of 4 seconds to perform mounting. Image data of the mounted sample (semiconductor chip / resin composition layer / semiconductor chip mounting substrate) was obtained using an ultrasonic precision flaw detection image processing device (μ-SDS (trade name), manufactured by KJTD Co., Ltd.), and the presence or absence of voids in the resin composition layer in the range of the semiconductor chip mounting part was confirmed from the image data. When the proportion of the area occupied by the part where voids were confirmed to the total area occupied by the resin composition layer in the range of the semiconductor chip mounting part was less than 5%, it was rated as A, when it was 5% or more but less than 10%, it was rated as B, when it was 10% or more but less than 20%, it was rated as C, and when it was 20% or more, it was rated as D. When the proportion of the area occupied by the part where voids were confirmed was less than 20%, the laminate was rated as having relatively high insulation reliability.

[0294] (4) Evaluation of voids after post-cure The laminates obtained in Examples 1 to 10 and Comparative Examples 1 to 5, each having a resin composition layer thickness of 35 μm, were cut into 8 mm×8 mm squares. Then, the laminates were arranged so that the resin composition layer of the cut laminate was in contact with the 15 μm copper circuit surface of the pad portion of the semiconductor chip mounting substrate (WALTS-KIT CC80(W)-0105JY (trade name) manufactured by Waltz Corporation), and laminated using a diaphragm-type vacuum laminator (V-130 (trade name), manufactured by Nikko Materials Co., Ltd.) under the conditions of a vacuum drawing time of 30 seconds, a temperature of 60° C., a pressure of 0.5 MPa, and a pressurization time of 60 seconds. Then, the polyethylene terephthalate film in the laminate in which the semiconductor chip mounting substrate and the resin composition layer were laminated was peeled off. Next, using a flip chip bonder (LFB-2301 (trade name), Shinkawa Co., Ltd.), a laminate consisting of a semiconductor chip mounting substrate and a resin composition layer was placed on a semiconductor chip having an electrode made of Cu pillars composed of copper and solder, so that the peeled surface of the resin composition layer was in contact with the semiconductor chip, and thermocompression bonded under conditions of a stage temperature of 85°C, a bond head temperature of 120°C, a load of 30N, and a time of 1 second, and then further thermocompression bonding was performed under conditions of a bond head temperature of 260°C, a load of 30N, and a time of 4 seconds for mounting. After mounting, a vacuum pressure oven (ELT-PIS (trade name), KeyLink) was used to bond the laminate at a pressure of 8 kgf / cm. 2 The temperature was raised to 140°C at 6°C / min under the above conditions, and the sample was held at 140°C for 30 minutes, and then heated to 200°C at 6°C / min, and then heated at 200°C for 2 hours to cure. Image data was obtained from the cured sample (semiconductor chip / resin composition layer / substrate for mounting semiconductor chip) using an ultrasonic precision flaw detection image processing device (μ-SDS (trade name), manufactured by KJTD Co., Ltd.), and the presence or absence of voids in the resin composition layer in the range of the semiconductor chip mounting part was confirmed from the image data. When the ratio of the area occupied by the part where voids were confirmed was less than 5% of the total area occupied by the resin composition layer in the range of the semiconductor chip mounting part, it was evaluated as A, when it was 5% or more and less than 10%, it was evaluated as B, and when it was 10% or more, it was evaluated as C. It should be noted that when the ratio of the area occupied by the part where voids were confirmed was less than 10%, the laminate was evaluated as having relatively high insulation reliability.

[0295] (5) Evaluation of chip adhesion after moisture absorption and reflow treatment The laminates obtained in Examples 1 to 10 and Comparative Examples 1 to 5, each having a resin composition layer thickness of 35 μm, were cut into 8 mm×8 mm squares. Then, the laminates were arranged so that the resin composition layer of the cut laminate was in contact with the 15 μm copper circuit surface of the pad portion of the semiconductor chip mounting substrate (WALTS-KIT CC80(W)-0105JY (trade name) manufactured by Waltz Corporation), and laminated using a diaphragm-type vacuum laminator (V-130 (trade name), manufactured by Nikko Materials Co., Ltd.) under the conditions of a vacuum drawing time of 30 seconds, a temperature of 60° C., a pressure of 0.5 MPa, and a pressurization time of 60 seconds. Then, the polyethylene terephthalate film in the laminate in which the semiconductor chip mounting substrate and the resin composition layer were laminated was peeled off. Next, using a flip chip bonder (LFB-2301 (trade name), Shinkawa Co., Ltd.), a laminate consisting of a semiconductor chip mounting substrate and a resin composition layer was placed on a semiconductor chip having an electrode made of Cu pillars composed of copper and solder, so that the peeled surface of the resin composition layer was in contact with the semiconductor chip, and thermocompression bonded under conditions of a stage temperature of 85°C, a bond head temperature of 120°C, a load of 30N, and a time of 1 second, and then further thermocompression bonding was performed under conditions of a bond head temperature of 260°C, a load of 30N, and a time of 4 seconds for mounting. After mounting, a vacuum pressure oven (ELT-PIS (trade name), KeyLink) was used to bond the laminate at a pressure of 8 kgf / cm. 2The temperature was raised to 140°C at 6°C / min under the above conditions, and the sample was held at 140°C for 30 minutes, and then heated to 200°C at 6°C / min, and then heated at 200°C for 2 hours to be cured. The cured sample (semiconductor chip / resin composition layer / substrate for mounting semiconductor chip) was heated and dried at a temperature of 125°C for 24 hours using a dryer (SPHH-201 (trade name) manufactured by ESPEC). The dried sample was humidified using a thermo-hygrostat (FX224C (trade name), manufactured by Kusumoto Chemical Co., Ltd.) under conditions of a temperature of 85°C, a relative humidity of 60%, and a humidification time of 168 hours. Thereafter, the humidified sample was heated using a reflow device (TNV50-568EM-P (trade name), manufactured by Tamura Corporation) to perform a moisture absorption reflow treatment. The temperature profile in the moisture absorption reflow treatment was in accordance with IPC / JEDEC J-STD-020. Only the semiconductor chip in the sample after the moisture absorption reflow treatment was removed using a rotary polishing machine (MetaServ (registered trademark) 3000 (product name), manufactured by Buehler) to obtain a laminate (A) including a resin composition layer and a semiconductor chip mounting substrate. In this laminate (A), the surface of the resin composition layer was visually observed, and the state of peeling was confirmed based on whether or not the wiring layer derived from the semiconductor chip was attached to the surface of the resin composition layer. When the wiring layer was attached to the entire surface of the resin composition layer, it was determined that no peeling had occurred and was evaluated as A. When the wiring layer was attached only to a part of the resin composition layer (i.e., there was a part of the resin composition layer to which the wiring layer was not attached), it was determined that a small amount of peeling had occurred and was evaluated as B. When the wiring layer derived from the semiconductor chip was removed from the resin composition layer during the semiconductor chip removal operation, it was determined that peeling had occurred and was evaluated as C. In addition, when the evaluation is A, the wiring layer derived from the semiconductor chip is not removed from the resin composition layer, and the chip adhesion is very excellent, so that the resin composition layer has high moisture absorption and heat resistance, and the laminate is evaluated to have very high insulation reliability.

[0296] [Table 1]

[0297] [Table 2] [Industrial Applicability]

[0298] The resin composition of the present embodiment is excellent in low void property, chip adhesion, and moisture absorption heat resistance, and is therefore suitable for use as a material for laminates, semiconductor chips with a resin composition layer, semiconductor chip mounting substrates with a resin composition layer, and semiconductor devices. The resin composition is suitable as an underfill material, and is more suitable as a preapplied underfill material.

Claims

1. One or more compounds (A) selected from the group consisting of maleimide compounds (AA) and citraconimide compounds (AB), allylphenol compounds (B), inorganic fillers (C), and comprising, a resin composition satisfying at least the following (i) and / or (ii). (i) Using a rheometer, the melt viscosity in the range of 40 to 260 °C was measured under the conditions of a measurement start temperature of 40 °C, a temperature increase rate of 10 °C / min, a frequency of 10.0 rad / s, and a strain of 0.1%, and the lowest melt viscosity obtained at that time is 100 Pa·s or less. (ii) The viscosity at 200 °C when measured using a rheometer under the conditions of a measurement start temperature of 40 °C, a temperature increase rate of 10 °C / min, a frequency of 10.0 rad / s, and a strain of 0.1% is 400 Pa·s or less.

2. The resin composition according to claim 1, wherein the maleimide compound (AA) comprises one or more selected from the group consisting of 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, 1,6-bis(maleimide)hexane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, a maleimide compound represented by the following formula (1), a maleimide compound represented by the following formula (2), a maleimide compound represented by the following formula (3), a bismaleimide compound containing a structural unit represented by the following formula (4) and maleimide groups at both ends of the molecular chain, a maleimide compound represented by the following formula (5), and a maleimide compound represented by the following formula (6). 【Chemical 1】 (In formula (1), R ８ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. R ９ each independently represents a hydrogen atom or a methyl group.) [Chemical 2] (In formula (2), R ５ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. R ６ each independently represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a —COOR group (R represents an alkyl group having 1 to 6 carbon atoms), or a hydrogen atom. n ２ represents an integer of 1 or more.) 【Chemical 3】 (In formula (3), n ３ represents an integer from 1 to 30.) 【Chemical Formula 4】 (In formula (4), R １１ represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R １２ represents a linear or branched alkylene group having 1 to 16 carbon atoms, or a linear or branched alkenylene group having 2 to 16 carbon atoms. R １３ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. n ５ represents an integer from 1 to 10.) 【Chemical Formula 5】 (In formula (5), R ７ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. n ４ represents an integer of 1 to 10.) 【Chemical Formula 6】 (In formula (6), R １０ each independently represents a hydrogen atom or a methyl group. n ５ represents an integer of 1 or more.).

3. The resin composition according to claim 1 or 2, wherein the maleimide compound (AA) comprises a maleimide compound containing a structural unit represented by the following formula (7) at the terminal in the molecule. 【Chemical Formula 7】 (In formula (7), R ８ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent, and at least one R ８ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group which may have a substituent. - * represents a hydrogen atom or a bond.).

4. The resin composition according to claim 2, wherein the maleimide compound (AA) comprises one or more selected from the group consisting of the maleimide compound represented by the formula (1) and the maleimide compound represented by the formula (3).

5. The compound (A) comprises a compound (A1) and a compound (A2), wherein the compound (A1) is one or more selected from the group consisting of a maleimide compound (AA-1) having a weight average molecular weight of 3,000 or more and 9,500 or less and a citraconimide compound (AB-1) having a weight average molecular weight of 3,000 or more and 9,500 or less, The compound (A2) is one or more selected from the group consisting of a maleimide compound (AA-2) having a weight average molecular weight of 300 or more and less than 3,000 and a citraconimide compound (AB-2) having a weight average molecular weight of 300 or more and less than 3,000, Each of the weight average molecular weights is a value in terms of standard polystyrene determined by the GPC (gel permeation chromatography) method. The resin composition according to claim 1 or 2.

6. The resin composition according to claim 1 or 2, wherein the allylphenol compound (B) contains an allylphenol compound (B1) represented by the following formula (8). [Chemical Formula 8] (In formula (8), W represents a divalent organic group having 1 to 15 carbon atoms which may have a substituent. R １ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aldehyde group, or a carboxy group. n represents an integer of 1 or more.).

7. The resin composition according to claim 6, wherein the allylphenol compound (B1) contains an allylphenol compound (B2) represented by the following formula (9). 【Chemical Formula 9】 (In formula (9), R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. n represents an integer of 1 or more.).

8. The resin composition according to claim 1 or 2, wherein the functional group equivalent ratio of the compound (A) to the allylphenol compound (B) ((equivalent of maleimide group of compound (A) + equivalent of citraconimide group of compound (A)) / equivalent of allyl group of allylphenol compound (B)) is 1 to 4.

9. The resin composition according to claim 1 or 2, wherein the inorganic filler (C) contains one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide.

10. The resin composition according to claim 1 or 2, wherein the average particle diameter of the inorganic filler (C) is 3 μm or less.

11. The resin composition according to claim 1 or 2, wherein the content of the inorganic filler (C) is 10 to 500 parts by mass with respect to 100 parts by mass in total of the compound (A) and the allylphenol compound (B).

12. The resin composition according to claim 1 or 2, further comprising a flux activator (D).

13. The resin composition according to claim 12, wherein the flux activator (D) contains a rosin-based resin.

14. The resin composition according to claim 1 or 2, which is for an underfill material.

15. A support substrate, A layer containing the resin composition according to claim 1 or 2 laminated on the support substrate, A laminate comprising:

16. The laminate according to claim 15, wherein the thickness of the layer containing the resin composition is 5 to 500 μm.

17. A semiconductor chip, A layer containing the resin composition according to claim 1 or 2 laminated on the semiconductor chip, A semiconductor chip with a resin composition layer, comprising...

18. A substrate for mounting a semiconductor chip, and A layer containing the resin composition according to Claim 1 or 2, laminated on the substrate for mounting a semiconductor chip, A substrate for mounting a semiconductor chip with a resin composition layer, comprising...

19. A semiconductor device comprising the semiconductor chip with a resin composition layer according to Claim 17.

20. A semiconductor device comprising the substrate for mounting a semiconductor chip with a resin composition layer according to Claim 18.

21. A semiconductor device comprising the semiconductor chip with a resin composition layer according to Claim 17 and the substrate for mounting a semiconductor chip with a resin composition layer according to Claim 18.

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