Thermosetting resin composition and semiconductor device

Abstract

To provide a thermosetting resin composition that makes it possible to achieve reduction in warpage of a substrate and achieve excellent moldability.SOLUTION: The inventive thermosetting resin composition contains epoxy resin, and benzoxazine resin. The thermosetting resin composition has a linear expansion coefficient α1 of 3 ppm / °C or higher and 16 ppm / °C or lower, measured with a thermomechanical analyzer in a temperature rise process of 50°C to 150°C.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a thermosetting resin composition and a semiconductor device. More specifically, the present invention relates to a thermosetting resin composition, a resin film, a resin film with a carrier and a prepreg using the same, and a semiconductor device. [Background technology]

[0002] In recent years, with the miniaturization and weight reduction of electronic devices, the study of thinning of semiconductor element mounting substrates such as lead frames is progressing. However, problems of warping of the lead frame are likely to occur after each process such as lamination of the adhesive film, resin sealing, and polishing of the sealing resin. For example, Patent Document 1 discloses an adhesive film for manufacturing electronic components, in which the adhesive layer contains a polyimide copolymer, the polyimide copolymer has at least an acid anhydride residue and a diamine residue, and the diamine residue contains 30 to 100 mol % of a polysiloxane-based diamine residue represented by general formula (1) in the total diamine residue, and the average linear expansion coefficient α (ppm / °C) of the heat-resistant film at 50 to 200°C and the average linear expansion coefficient β (ppm / °C) of the sealing resin at 50 to 200°C are controlled. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-136600 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, according to the study of the present inventors, it was newly discovered that in the conventional technology, when wire bonding is performed on an electrode pad arranged on a sealing resin embedded in a metal plate, the electrode pad may sink into the sealing resin. As a result, there is room for improvement in obtaining a semiconductor device with high precision. In addition, from the viewpoint of obtaining a semiconductor device with higher precision, there is a need to improve the reduction of warping of the metal plate. [Means for solving the problem]

[0005] In order to solve the two problems of suppressing the warping of the substrate and the sinking of the electrode pads, the inventors of the present invention have focused on the sealing resin material and conducted research, and have found that it is effective to use epoxy resin and benzoxazine resin as the sealing material and control their linear expansion coefficients. In other words, they have found that a combination of epoxy resin and benzoxazine resin as types of resin material while using a specific linear expansion coefficient as an index is effective in achieving both of these two different problems, and have completed the present invention.

[0006] The present invention relates to A thermosetting resin composition comprising an epoxy resin and a benzoxazine resin, Provided is a thermosetting resin composition having a linear expansion coefficient α1 of 3 ppm / °C or more and 16 ppm / °C or less, as measured using a thermomechanical analyzer during a temperature rise process from 50°C to 150°C.

[0007] The present invention provides a resin film made of the above-mentioned thermosetting resin composition.

[0008] The present invention relates to A carrier substrate; The present invention provides a resin film with a carrier, comprising: a resin film formed on the carrier base material and made of the above-mentioned thermosetting resin composition.

[0009] The present invention relates to A prepreg is provided by impregnating a fiber substrate with the above thermosetting resin composition.

[0010] The present invention relates to A semiconductor element provided on a substrate; a bonding wire connected to the semiconductor element; an electrode pad electrically connected to the bonding wire; Equipped with The present invention provides a semiconductor device, in which the electrode pads are disposed on a cured product of the above-mentioned thermosetting resin composition. Effect of the Invention

[0011] According to the present invention, it is possible to provide a thermosetting resin composition which reduces warpage of a substrate and provides good moldability. [Brief description of the drawings]

[0012] [Figure 1] 1 is a schematic cross-sectional view showing an example of a semiconductor device according to an embodiment of the present invention; [Diagram 2] 5A to 5C are cross-sectional views showing process steps of an example of a method for manufacturing the semiconductor device according to the present embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In all the drawings, the same components are given the same reference numerals, and the description will be omitted as appropriate. In this specification, the expression "a to b" in the explanation of a numerical range means from a to b, unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass to 5% by mass."

[0014] <Semiconductor device> FIG. 1 is a schematic cross-sectional view showing an example of the semiconductor device of the present embodiment. The semiconductor device 100 of this embodiment comprises a semiconductor element 31 provided on a substrate (lead frame 12), a bonding wire 41 connected to the semiconductor element 31, and an electrode pad 30 electrically connected to the bonding wire 41, with the electrode pad 30 being disposed on a cured product of the thermosetting resin 20 of this embodiment, which will be described later.

[0015] According to the thermosetting resin composition of the present embodiment, it is possible to suppress sinking of the electrode pad during wire bonding and to suppress warping of the substrate, which results in a semiconductor device being manufactured with high accuracy.

[0016] <Method of Manufacturing Semiconductor Device> First, an example of a method for manufacturing the semiconductor device of this embodiment will be described. The method for manufacturing a semiconductor device using the thermosetting resin composition of this embodiment is appropriately selected depending on the application, etc., but below, a method for manufacturing a semiconductor device in which a lead frame is used as a substrate and the thermosetting resin composition is used to embed the lead frame will be described.

[0017] 2A to 2C are cross-sectional views illustrating steps in one example of a method for manufacturing the semiconductor device of this embodiment.

[0018] 2(a), a metal plate 10 is prepared. The metal plate 10 will later become a lead frame 12. Examples of the metal constituting the metal plate 10 include one or more selected from copper, copper alloys, aluminum, aluminum alloys, nickel, iron, tin, and the like. Among these, the metal plate 10 is preferably a copper layer or an aluminum layer, and more preferably a copper layer. By using copper or aluminum, the circuit processability of the metal plate 10 can be improved. The metal plate 10 may be a metal foil available in a plate shape, or a metal foil available in a roll shape.

[0019] The lower limit of the thickness of the metal plate 10 is, for example, 0.01 mm or more, preferably 0.05 mm or more, and more preferably 0.10 mm or more. If the thickness is equal to or more than this value, heat generation in the circuit pattern can be suppressed even in applications requiring high current. The upper limit of the thickness of the metal plate 10 is, for example, 2.0 mm or less, preferably 1.5 mm or less, and more preferably 1.0 mm or less. If the thickness is less than such a numerical value, the circuit processability can be improved, and the substrate as a whole can be made thinner.

[0020] 2(b), a predetermined circuit pattern 11 is formed on one surface (front surface) of the metal plate 10. The method for forming the circuit pattern 11 is not particularly limited, and a known method can be used. That is, a part of the metal plate 10 is removed by etching, and the metal plate 10 having the predetermined circuit pattern 11 can be formed.

[0021] 2(c), the thermosetting resin composition 20 of this embodiment is laminated (placed) on the metal plate 10 at 100 to 130°C by a vacuum laminator so as to embed the circuit pattern 11. At this time, by using the thermosetting resin composition 20 of this embodiment, the filling property to the circuit pattern 11 can be improved and the generation of voids can be reduced. Then, the thermosetting resin composition 20 is cured by performing a heat treatment in an oven. The curing conditions can be, for example, 180 to 220°C and 50 to 80 minutes. At this time, thermal shrinkage due to curing occurs, but by using the thermosetting resin composition 20 of this embodiment, the difference in the linear expansion coefficient between the thermosetting resin composition 20 and the metal plate 10 can be reduced in the range from the temperature at the time of curing of the thermosetting resin composition 20 to room temperature, and warping of the metal plate 10 can be suppressed.

[0022] 2(d), a part of the cured product of the thermosetting resin composition 20 is polished to expose the upper surface of the circuit pattern 11. The polishing method is not particularly limited, but examples thereof include laser processing, chemical polishing, and mechanical polishing. By using the thermosetting resin composition 20 of the present embodiment, the elasticity of the cured product of the thermosetting resin composition 20 can be increased.

[0023] Next, the other surface (rear surface) of the metal plate 10 is etched to expose the cured product of the thermosetting resin composition 20 embedded in the circuit pattern 11 on the other surface side of the metal plate 10, and further, an electrode pad 30 is formed on the cured product of the thermosetting resin composition 20. A known method can be used as the etching method. At this time, since the circuit pattern 11 is filled with the cured product of the thermosetting resin composition 20 of this embodiment, warping caused by etching of the metal plate 10 can be suppressed.

[0024] Thereafter, the semiconductor element 31 and the electrode pads 30 are connected by bonding wires 41, as shown in FIG. Here, in order to electrically connect the bonding wire 41 and the electrode pad 30, the tip of the bonding wire 41 is pressed against the electrode pad 30, the tip of the bonding wire 41 is melted, and ultrasonic vibration or the like is applied to the tip. Here, the inventors of the present invention have noticed that when a load is applied to the electrode pad 30 from the bonding wire 41, the electrode pad 30 sinks slightly into the cured product of the thermosetting resin composition 20. It has been found that a semiconductor device with higher accuracy can be obtained by reducing such sinking.

[0025] Examples of materials constituting the bonding wire 41 include gold, copper, and aluminum, but copper is preferred in terms of conductivity and cost. In addition, copper is harder than gold and aluminum, so that a load is likely to be applied to the electrode pad during the wire bonding process. Therefore, by using the thermosetting resin composition of this embodiment, even if copper is used as the material constituting the bonding wire 41, it is possible to suppress the sinking of the electrode pad 30 and obtain a semiconductor device with high accuracy.

[0026] Then, by using a known method, the semiconductor chip 31 provided on the substrate (lead frame 12) made of the metal plate 10 is resin-sealed to obtain a semiconductor device 100 in which the semiconductor chip 31 is encapsulated by the encapsulant 42 (Figure 1).

[0027] <Thermosetting resin composition> Next, the thermosetting resin composition of the present embodiment will be described. The thermosetting resin composition of the present embodiment contains an epoxy resin and a benzoxazine resin, and has a linear expansion coefficient α1 of 3 ppm / °C or more and 16 ppm / °C or less, as measured using a thermomechanical analyzer during a temperature rise process from 50°C to 150°C. This effectively reduces warping of the substrate.

[0028] In this embodiment, the linear expansion coefficient α1 is 3 ppm / °C or more and 16 ppm / °C or less, preferably 5 ppm / °C or more and 15 ppm / °C or less, more preferably 8 ppm / °C or more and 14.5 ppm / °C or less, and even more preferably 9 ppm / °C or more and 13.5 ppm / °C or less. By setting the linear expansion coefficient α1 within the above numerical range, the difference in linear expansion coefficient with the copper plate is reduced, making it easier to suppress warping of the board.

[0029] In addition, in the thermosetting resin composition of the present embodiment, when the minimum value η of the complex dynamic viscosity in a dynamic viscoelasticity test of a resin film made of the thermosetting resin composition in a B-stage state is defined as a measurement range of 50 to 200°C, a heating rate of 3°C / min, and a frequency of 62.83 rad / sec, it is preferable that η is 1 Pa s or more and 2000 Pa s or less. This improves the elasticity of the thermosetting resin composition, makes it easier to reduce embedding of the electrode pads, and provides good moldability of the semiconductor package. The η is 100 Pa·s or more and 5000 Pa·s or less, preferably 500 to 4500, and more preferably 750 to 4000 Pa·s. The resin film will be described in detail later.

[0030] The linear expansion coefficient α1 and the minimum value η of the complex dynamic viscosity in this embodiment can be controlled by selecting the resin material and the inorganic filler and adjusting the content thereof.

[0031] Hereinafter, each component contained in the thermosetting resin composition of the present embodiment will be described.

[0032] [Epoxy resin] As the epoxy resin, any monomer, oligomer or polymer having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure thereof are not particularly limited. In the present embodiment, examples of the epoxy resin include biphenyl-type epoxy resins; bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and tetramethylbisphenol F-type epoxy resins; stilbene-type epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; multifunctional epoxy resins such as triphenolmethane-type epoxy resins and alkyl-modified triphenolmethane-type epoxy resins; aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins having a phenylene skeleton, phenol aralkyl-type epoxy resins having a biphenylene skeleton, and biphenyl aralkyl-type epoxy resins; naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by glycidyl etherifying a dimer of dihydroxynaphthalene; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; and bridged cyclic hydrocarbon compound-modified phenol-type epoxy resins such as dicyclopentadiene-modified phenol-type epoxy resins. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving the balance between moisture resistance reliability and moldability, the epoxy resin preferably contains one or more types selected from the group consisting of bisphenol type epoxy resins, novolac type epoxy resins, biphenyl aralkyl type epoxy resins, biphenyl type epoxy resins, phenol aralkyl type epoxy resins, and triphenol methane type epoxy resins, and more preferably contains at least one type selected from the group consisting of biphenyl aralkyl type epoxy resins, biphenyl type epoxy resins, and phenol aralkyl type epoxy resins.

[0033] It is more preferable to use, as the epoxy resin (A), one containing at least one selected from the group consisting of an epoxy resin represented by the following formula (1), an epoxy resin represented by the following formula (2), and an epoxy resin represented by the following formula (3).

[0034] [ka] (In formula (1), Ar 1 represents a phenylene group or a naphthylene group, Ar 1 When Ar is a naphthylene group, the glycidyl ether group may be bonded to either the α-position or the β-position. 2 R represents any one of a phenylene group, a biphenylene group, and a naphthylene group. a and R b each independently represents a hydrocarbon group having 1 to 10 carbon atoms; g is an integer of 0 to 5, and h is an integer of 0 to 8. 3 represents the degree of polymerization, the average value of which is 1 to 3.)

[0035] [ka] (In formula (2), there are multiple R c Each of n independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. 5 represents the degree of polymerization, the average value of which is 0 to 4.)

[0036] [ka] (In formula (3), there are multiple R d and R e Each of n independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. 6 represents the degree of polymerization, the average value of which is 0 to 4.)

[0037] In this embodiment, the content of the epoxy resin in the thermosetting resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, when the entire thermosetting resin composition is taken as 100% by mass. By making the content of the epoxy resin equal to or more than the above lower limit, sufficient fluidity can be achieved during molding, and filling properties and moldability can be improved. On the other hand, the content of the epoxy resin in the thermosetting resin composition is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, when the entire thermosetting resin composition is taken as 100% by mass. By making the content of the epoxy resin equal to or less than the above upper limit, it is possible to improve the moisture resistance reliability and reflow resistance of the cured product of the thermosetting resin composition.

[0038] [Benzoxazine resin] The benzoxazine resin of the present embodiment is a (co)polymer of a compound having two or more benzoxazine rings. From the viewpoint of improving heat resistance, the compound having two or more benzoxazine rings may contain at least one of the compound shown in the following general formula (4) and the compound shown in the following general formula (4), and preferably contains at least the compound shown in the following general formula (4).

[0039] [ka]

[0040] In the above general formula (4), R 3 is a divalent organic group having 1 to 30 carbon atoms, and may contain at least one of an oxygen atom and a nitrogen atom. From the viewpoint of improving the high-temperature storage properties of the encapsulating material, R 3 is preferably an organic group containing an aromatic ring. In this embodiment, as the compound represented by the above general formula (4), for example, a compound represented by the following formula (4a) can be used.

[0041] [ka]

[0042] [ka]

[0043] In the above general formula (5), R 4is a divalent organic group having 1 to 30 carbon atoms, and may contain one or more of an oxygen atom, a nitrogen atom, and a sulfur atom. 5 are each independently an aromatic hydrocarbon group having 1 to 12 carbon atoms.

[0044] In the present embodiment, the content of the benzoxazine resin in the thermosetting resin composition is preferably 8% by mass or more, and more preferably 10% by mass or more, when the entire thermosetting resin composition is taken as 100% by mass. By making the content of the benzoxazine resin equal to or more than the above lower limit, it is possible to improve filling property and moldability. On the other hand, the content of the benzoxazine resin in the thermosetting resin composition is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less, when the entire thermosetting resin composition is taken as 100% by mass. By keeping the content of the benzoxazine resin at the above upper limit or less, good elasticity can be maintained in the cured product of the thermosetting resin composition.

[0045] [Cyanate resin] The thermosetting resin composition of the present embodiment preferably contains a cyanate resin. The cyanate resin makes it easier to obtain a low thermal expansion coefficient, a low dielectric constant, and a low dielectric tangent. In addition, the peel strength can be improved, and the heat resistance can be improved.

[0046] The cyanate resin is preferably an aromatic cyanate resin, and specific examples thereof include novolac-type cyanate resins such as phenol novolac-type and cresol novolac-type cyanate resins; aralkyl-type cyanate resins such as phenyl aralkyl-type, biphenyl aralkyl-type and naphthalene aralkyl-type cyanate resins; and bisphenol-type cyanate resins such as bisphenol A-type cyanate resin, bisphenol E-type cyanate resin and tetramethyl bisphenol F-type cyanate resin. Among these, bisphenol-type cyanate and / or novolac-type cyanate resins are preferred, and it is more preferred to use both in combination. The reason for this is that bisphenol-type cyanate ester resins have fewer crosslinking points, so that when triazine rings are formed, unreacted cyanate groups are less likely to remain, and it is easier to maintain good dielectric properties. In addition, novolac-type cyanate resins form triazine rings after the curing reaction, so that rigidity and heat resistance can be improved.

[0047] As the novolac type cyanate resin, for example, one represented by the following formula (I) can be used.

[0048] [ka]

[0049] The average repeating unit n of the novolac cyanate resin represented by the general formula (I) is any integer. The average repeating unit n is not particularly limited, but is preferably 1 or more, more preferably 2 or more. When the average repeating unit n is equal to or more than the above lower limit, the heat resistance of the novolac cyanate resin is improved, and the elimination and volatilization of low molecular weight compounds during heating can be suppressed. In addition, the average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. When n is equal to or less than the above upper limit, the melt viscosity can be suppressed from increasing, and the moldability of the prepreg can be improved.

[0050] The cyanate resin may be modified, for example, it may contain butadiene-modified cyanate modified with butadiene. Specifically, the butadiene-modified cyanate may be obtained by mixing a cyanate ester compound with polybutadiene and then subjecting it to thermal polymerization, and / or by mixing a polymer of a cyanate ester compound with polybutadiene and then subjecting it to thermal polymerization. This allows the heat resistance to be well maintained while achieving both dielectric properties and low warpage.

[0051] The lower limit of the weight average molecular weight (Mw) of the cyanate resin is not particularly limited, but is preferably at least Mw 500, and more preferably at least Mw 600. When Mw is at least the above lower limit, the occurrence of tackiness can be suppressed when a prepreg is produced, and the prepregs can be suppressed from adhering to each other when they come into contact with each other, or from transferring. In addition, the upper limit of Mw is not particularly limited, but is preferably Mw 4,500 or less, and more preferably Mw 3,000 or less. When Mw is equal to or less than the upper limit, the cyclization reaction of the cyanate resin (C) can be prevented from accelerating, and defects in the insulating layer and a decrease in the peel strength between the insulating layer and the metal layer can be prevented.

[0052] The Mw of the cyanate resin can be measured, for example, by GPC (gel permeation chromatography, standard substance: polystyrene equivalent).

[0053] In addition, the cyanate resin may be used alone or in combination of two or more types having different Mw, or in combination of one or more types and their prepolymers.

[0054] In this embodiment, the content of the cyanate resin in the thermosetting resin composition is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, and particularly preferably 0.3 mass% or more, when the entire thermosetting resin composition is 100 mass%. On the other hand, the content of the cyanate resin in the thermosetting resin composition is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 2 mass% or less, when the entire thermosetting resin composition is 100 mass%.

[0055] [Inorganic filler] The thermosetting resin composition of the present embodiment preferably contains an inorganic filler, which can provide a low linear expansion coefficient, suppress water absorption, and increase mechanical strength.

[0056] Examples of inorganic fillers in this embodiment include silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, and calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride; and titanates such as strontium titanate and barium titanate. Among these, titanium oxide, talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide are preferred, and titanium oxide and silica are more preferred. As the inorganic filler, one of these may be used alone, or two or more of them may be used in combination.

[0057] The lower limit of the average particle size of the inorganic filler is not particularly limited, but may be, for example, 0.01 μm or more, 0.1 μm or more, or 0.5 μm or more, which can prevent the viscosity of the varnish using the thermosetting resin composition of the present embodiment from increasing, and can improve the workability during embedding. The upper limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, and even more preferably 1.5 μm or less, for example, which can suppress the phenomenon of settling of the inorganic filler in the thermosetting resin varnish, thereby obtaining a more uniform resin film.

[0058] The inorganic filler is not particularly limited, but may be an inorganic filler having a monodisperse average particle size, or may be an inorganic filler having a polydisperse average particle size. Furthermore, one or more inorganic fillers having monodisperse and / or polydisperse average particle sizes may be used in combination. In the case of polydisperse, it is preferable that the particle size distribution measured by the laser diffraction scattering method has peaks in the particle size ranges of 0.001 to 0.1 μm and 0.5 to 3 μm, respectively.

[0059] In this embodiment, the average particle diameter of the inorganic filler can be determined by measuring the particle size distribution of the particles on a volume basis using, for example, a laser diffraction particle size distribution measuring device (LA-500, manufactured by HORIBA Corporation), and taking the median diameter (D50) as the average particle diameter.

[0060] The lower limit of the content of the inorganic filler is not particularly limited, but is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and even more preferably 70 parts by mass or more, based on 100 parts by mass of the total solid content of the resin composition. This allows the cured resin film to have a particularly low thermal expansion, and suppresses warping of the semiconductor package. On the other hand, the upper limit of the content of the inorganic filler is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 85 parts by mass or less, based on 100 parts by mass of the total solid content of the resin composition, which improves the handleability and makes it easier to form a resin film.

[0061] [Other additives] The thermosetting resin composition of the present embodiment may contain, as necessary, additives such as a colorant, a coupling agent, a curing accelerator, a curing agent, a thermoplastic resin, and an organic filler. The thermosetting resin composition of the present embodiment may be suitably used in a liquid form in which the above components are dissolved and / or dispersed in an organic solvent or the like.

[0062] (Coloring agent) The colorant may be, for example, one or more selected from black titanium oxide, pitch, and carbon black. By using these, it is possible to prevent the colorant from absorbing the laser energy excessively during laser marking. This makes it possible to prevent the mark from being excessively deep due to the loss of the colorant by the laser. Carbonization is also easily suppressed.

[0063] Black titanium oxide is Ti n O (2n-1) (n is a positive integer). The black titanium oxide Ti n O (2n-1) It is preferable to use a colorant having n of 4 or more and 6 or less. By making n 4 or more, the dispersibility of the colorant can be improved. On the other hand, by making n 6 or less, the laser marking property can be improved. Here, the colorant is black titanium oxide, Ti 4 O 7 , Ti 5 O 9 , and Ti 6 O 11 It is preferable to include at least one of the following: Pitch is a residue obtained by distilling tar obtained by dry distillation of organic substances such as petroleum, coal, and wood. The pitch used as a colorant is not particularly limited, but may be, for example, petroleum pitch or coal pitch. As the pitch, isotropic pitch, mesophase pitch, or mesophase spheres produced by cooling mesophase pitch and separated as an insoluble component of quinoline may be used. Among these, it is more preferable to use mesophase spheres from the viewpoint of improving the laser marking property and dispersibility in the encapsulating resin composition.

[0064] (Coupling Agent) The coupling agent is used to improve the wettability at the interface between the thermosetting resin and the inorganic filler, and to fix the resin composition uniformly to the fiber substrate.

[0065] As the coupling agent of the present embodiment, any one that is normally used as a coupling agent can be used, but specifically, it is preferable to use one or more coupling agents selected from epoxy silane coupling agents, cationic silane coupling agents, amino silane coupling agents, titanate coupling agents, and silicone oil coupling agents. This can increase the wettability with the interface of the filler, thereby further improving heat resistance.

[0066] The lower limit of the content of the coupling agent is not particularly limited since it depends on the specific surface area of ​​the inorganic filler, but for example, it is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the inorganic filler. By making the content of the coupling agent equal to or more than the lower limit, the inorganic filler can be sufficiently coated, and the heat resistance can be easily improved. On the other hand, by making the content of the coupling agent equal to or less than the upper limit, a good reaction can be maintained, and good bending strength can be obtained. The content of the coupling agent is preferably from 0.05 to 3 mass %, and more preferably from 0.1 to 2 mass %, based on the thermosetting resin composition.

[0067] (Cure accelerator) As the curing accelerator of the present embodiment, a known one can be used. For example, organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, cobalt bisacetylacetonate (II), and cobalt trisacetylacetonate (III) are included; tertiary amines such as triethylamine, tributylamine, and diazabicyclo[2,2,2]octane; imidazoles such as 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, and 2-phenyl-4,5-dihydroxyimidazole; phenolic compounds such as phenol, bisphenol A, and nonylphenol; organic acids such as acetic acid, benzoic acid, salicylic acid, and paratoluenesulfonic acid; onium salt compounds, and derivatives thereof. These may be used alone or in combination of two or more. Among them, imidazole and onium salt compounds are preferable from the viewpoint of stably improving the resin curing property. Such onium salt compounds are not particularly limited, but examples thereof include onium salt compounds represented by the following formula (IX).

[0068] [ka]

[0069] In formula (IX), P represents a phosphorus atom, R 1 , R 2 , R 3 and R 4 A each represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group, and may be the same or different. - represents an anion of a proton donor having a valence of n (n≧1) and having at least one proton that can be released outside the molecule, or a complex anion thereof.

[0070] The lower limit of the content of the curing accelerator is not particularly limited, but is preferably 0.005 to 5 mass %, and more preferably 0.01 to 2 mass %, of the entire resin composition. By making the content of the curing accelerator equal to or more than the above lower limit, a good curing acceleration effect can be obtained, while by making the content of the curing accelerator equal to or more than the above lower limit, the prepreg can be kept in a good state of preservation.

[0071] <Varnish> In this embodiment, the varnish-like thermosetting resin composition may contain a solvent. Examples of the solvent include organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene glycol, cellosolve-based solvents, carbitol-based solvents, anisole, and N-methylpyrrolidone. These may be used alone or in combination of two or more kinds.

[0072] When the resin composition is in the form of a varnish, the solid content of the resin composition may be, for example, 30% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 70% by mass or less, which results in a resin composition with excellent workability and film-forming properties.

[0073] The varnish-like resin composition can be prepared by dissolving, mixing, and stirring the above-mentioned components in a solvent using various mixers such as those used in an ultrasonic dispersion system, a high-pressure collision dispersion system, a high-speed rotation dispersion system, a bead mill system, a high-speed shear dispersion system, and a rotation-revolution dispersion system.

[0074] Hereinafter, an example in which the thermosetting resin composition of the present embodiment is used will be described.

[0075] <Resin film> Next, the resin film of this embodiment will be described. The resin film of this embodiment can be obtained by forming the above-mentioned resin composition in a varnish form into a film. For example, the resin film of this embodiment can be obtained by removing the solvent from a coating film obtained by applying the resin composition in a varnish form. In such a resin film, the solvent content can be 5 mass % or less with respect to the entire resin film. In this embodiment, the step of removing the solvent may be carried out under conditions of, for example, 100°C to 150°C and 1 minute to 5 minutes. This makes it possible to sufficiently remove the solvent while suppressing the progress of curing of the resin film containing a thermosetting resin.

[0076] The resin film of the present embodiment may be composed of a resin film alone, or may be composed so as to include a fiber base material therein.

[0077] <Prepreg> The prepreg of the present embodiment is configured to contain a fibrous base material in a resin composition. The prepreg is obtained by impregnating a fibrous base material with the resin composition. For example, prepreg can be used as a sheet-like material obtained by impregnating a fiber substrate with a resin composition and then semi-curing it. A sheet-like material having such a structure has excellent properties such as dielectric properties and mechanical and electrical connection reliability under high temperature and humidity, and is suitable for producing an insulating layer of a printed wiring board.

[0078] In this embodiment, the method of impregnating the resin composition into the fiber substrate is not particularly limited, but examples thereof include a method of dissolving the resin composition in a solvent to prepare a resin varnish and immersing the fiber substrate in the resin varnish, a method of applying the resin varnish to the fiber substrate using various coaters, a method of spraying the resin varnish onto the fiber substrate using a sprayer, and a method of laminating both sides of the fiber substrate with the resin film consisting of the resin composition.

[0079] Examples of the fiber substrate include glass fiber substrates such as woven glass cloth and nonwoven glass cloth, inorganic fiber substrates such as woven or nonwoven cloth containing inorganic compounds other than glass as components, and organic fiber substrates composed of organic fibers such as aromatic polyamideimide resin, polyamide resin, aromatic polyester resin, polyester resin, polyimide resin, and fluororesin. Among these substrates, the use of a glass fiber substrate typified by glass woven cloth in terms of strength can improve the mechanical strength and heat resistance of the printed wiring board.

[0080] The thickness of the fiber base material is not particularly limited, but is preferably 5 μm to 150 μm, more preferably 10 μm to 100 μm, and even more preferably 12 μm to 90 μm. By using a fiber base material having such a thickness, the handleability during prepreg production can be further improved. When the thickness of the fiber substrate is equal to or less than the upper limit, the impregnation of the resin composition in the fiber substrate is improved, and the occurrence of strand voids and deterioration of insulation reliability can be suppressed. In addition, the formation of through holes by carbon dioxide, UV, excimer, or other lasers can be facilitated. In addition, when the thickness of the fiber substrate is equal to or more than the lower limit, the strength of the fiber substrate and prepreg can be improved. As a result, the handling property can be improved, the preparation of prepreg can be facilitated, and warping of the resin substrate can be suppressed.

[0081] As the above-mentioned glass fiber substrate, for example, a glass fiber substrate formed of one or more types of glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass is suitably used.

[0082] In this embodiment, the prepreg can be used to form, for example, an insulating layer in a build-up layer or an insulating layer in a core layer of a printed wiring board. When the prepreg is used to form an insulating layer in a core layer of a printed wiring board, for example, two or more prepregs can be stacked and the resulting laminate can be heat-cured to form an insulating layer for the core layer.

[0083] <Metal-clad laminate> The laminate of the present embodiment is a metal-clad laminate in which a metal layer is disposed on at least one surface of the cured product of the prepreg.

[0084] A method for producing a metal-clad laminate using a prepreg is, for example, as follows. A metal foil is placed on both the upper and lower sides or one side of the outer side of a prepreg or a laminate of two or more prepregs, and these are bonded under high vacuum conditions using a laminator or Becquerel device, or a metal foil is placed on both the upper and lower sides or one side of the outer side of the prepreg as is. When two or more prepregs are laminated, a metal foil is placed on both the upper and lower sides or one side of the outermost side of the laminated prepregs. Next, a metal-clad laminate can be obtained by hot-press molding the laminate of the prepreg and the metal foil. Here, it is preferable to continue pressing until the end of cooling during hot-press molding.

[0085] Examples of the metals constituting the metal foil include copper, copper-based alloys, aluminum, aluminum-based alloys, silver, silver-based alloys, gold, gold-based alloys, zinc, zinc-based alloys, nickel, nickel-based alloys, tin, tin-based alloys, iron, iron-based alloys, Fe-Ni-based alloys such as Kovar (trade name), 42 alloy, Invar, and Super Invar, W, and Mo. Among these, the metal constituting the metal foil 105 is preferably copper or a copper alloy because it has excellent conductivity, is easy to form a circuit by etching, and is inexpensive. That is, the metal foil 105 is preferably copper foil. As the metal foil, a metal foil with a carrier can also be used. The thickness of the metal foil is preferably 0.5 μm or more and 20 μm or less, and more preferably 1.5 μm or more and 18 μm or less.

[0086] <Resin film with carrier> Next, the resin film with a carrier of this embodiment will be described.

[0087] An example of the resin film with a carrier includes a carrier base material and a resin film made of a resin composition provided on the carrier base material. The resin film may be in a roll shape that can be wound up, or in a rectangular sheet shape.

[0088] As the carrier substrate, for example, a polymer film or a metal foil can be used. The polymer film is not particularly limited, but examples thereof include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, release paper such as silicone sheets, and thermoplastic resin sheets having heat resistance such as fluorine-based resins and polyimide resins. The metal foil is not particularly limited, but examples thereof include copper and / or copper-based alloys, aluminum and / or aluminum-based alloys, iron and / or iron-based alloys, silver and / or silver-based alloys, gold and gold-based alloys, zinc and zinc-based alloys, nickel and nickel-based alloys, and tin and tin-based alloys. Among these, a sheet made of polyethylene terephthalate is most preferable because it is inexpensive and the peel strength can be easily adjusted. This makes it easy to peel off the resin film with the carrier with an appropriate strength.

[0089] The thickness of the carrier substrate is not particularly limited, but may be, for example, 10 to 100 μm, or 10 to 70 μm, which is preferable because it improves the handleability when producing a resin film with a carrier.

[0090] The resin film of the carrier-attached resin film of the present embodiment may be a single layer or a multilayer, and may be composed of one or more types of films. When the resin sheet is a multilayer, it may be composed of the same type or different types.

[0091] The lower limit of the thickness of the resin film is, for example, 5 μm or more, and preferably 20 μm or more. This can improve the insulation reliability. On the other hand, the upper limit of the thickness of the resin film is, for example, 200 μm or less, and preferably 100 μm or less. This can realize a thin-layered printed wiring board. In addition, by setting the thickness of the resin film within the above range, when manufacturing a printed wiring board, it is possible to fill the unevenness of the inner layer circuit and mold it, and also to ensure a suitable thickness of the insulating resin layer of the build-up layer.

[0092] The surface of the resin film with carrier may be exposed or may be covered with a protective film (cover film). As the protective film, a film having a known protective function may be used, for example, a PET film may be used. For example, the resin film may be formed between the carrier substrate and the cover film. This improves the handling property of the resin film.

[0093] <Printed wiring board> The printed wiring board of this embodiment includes an insulating layer made of the cured product of the above-mentioned resin film (cured product of the resin composition). In this embodiment, the cured resin film can be used, for example, as a build-up layer of a normal printed wiring board, a build-up layer in a printed wiring board having no core layer, a build-up layer of a coreless substrate used in PLP, a build-up layer of an MIS substrate, etc. The insulating layer constituting such a build-up layer can also be suitably used as a build-up layer constituting a large-area printed wiring board used to collectively produce a plurality of semiconductor packages.

[0094] In the present embodiment, the resin film made of the resin composition for forming the insulating film may be impregnated with glass fibers. In a semiconductor package using such a resin film as a build-up layer, the linear expansion coefficient of the cured resin film can be reduced, so that package warpage can be sufficiently suppressed.

[0095] Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. Below, examples of reference forms are given. 1. A thermosetting resin composition comprising an epoxy resin and a benzoxazine resin, A thermosetting resin composition having a linear expansion coefficient α1 of 3 ppm / °C or more and 16 ppm / °C or less, as measured using a thermomechanical analyzer during a temperature rise process from 50°C to 150°C. 2. The thermosetting resin composition according to 1., A thermosetting resin composition, wherein when a dynamic viscoelasticity test of a resin film made of the thermosetting resin composition in a B-stage state is performed, the complex dynamic viscosity η is defined as the minimum value η within a measurement range of 50 to 200°C, a heating rate of 3°C / min, and a frequency of 62.83 rad / sec, and η is 100 Pa s or more and 5000 Pa s or less. 3. The thermosetting resin composition according to 1. or 2., The thermosetting resin composition further comprises an inorganic filler. 4. The thermosetting resin composition according to 3., The thermosetting resin composition, wherein the inorganic filler comprises silica. 5. The thermosetting resin composition according to 3. or 4., A thermosetting resin composition, wherein the content of the inorganic filler is 60% by mass or more and 95% by mass or less based on the total mass of the thermosetting resin composition. 6. The thermosetting resin composition according to any one of 1. to 5., The thermosetting resin composition further comprises a cyanate resin. 7. A resin film comprising the thermosetting resin composition described in any one of 1. to 6. 8. A carrier substrate; A resin film with a carrier, comprising: a resin film formed on the carrier base material and made of the thermosetting resin composition according to any one of 1. to 6. 9. A prepreg obtained by impregnating a fiber substrate with the thermosetting resin composition described in any one of 1. to 6. 10. A semiconductor element provided on a substrate; a bonding wire connected to the semiconductor element; an electrode pad electrically connected to the bonding wire; Equipped with 7. A semiconductor device, comprising: a semiconductor device having an electrode pad disposed on a cured product of the thermosetting resin composition according to any one of 1. to 6. EXAMPLES

[0096] Next, the present invention will be described in detail with reference to examples, but the content of the present invention is not limited to the examples.

[0097] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the descriptions of these examples.

[0098] 1) Preparation of thermosetting resin composition Each component was dissolved or dispersed at the solid content shown in Table 1, and the non-volatile content was adjusted to 70 mass% with methyl ethyl ketone. The mixture was then stirred using a high-speed stirrer to prepare a varnish-like thermosetting resin composition (resin varnish P).

[0099] The numerical values ​​showing the blending ratio of each component in Table 1 indicate the blending ratio (mass %) of each component relative to the total solid content of the resin composition.

[0100] (raw materials) Details of the raw materials for each component in Table 1 are as follows: Inorganic filler 1: Silica particles (Admatechs, SC4050, average particle size 1.1 μm) Inorganic filler 2: Silica nanoparticles (Admatechs, Admanano, average particle size 55 nm) Benzoxazine resin: Pd-type benzoxazine represented by the above formula (4a) (manufactured by Shikoku Kasei Co., Ltd.) Epoxy resin 1: Biphenyl aralkyl type epoxy resin "NC-3000H" manufactured by Nippon Kayaku Co., Ltd. Epoxy resin 2: Bisphenol F type epoxy resin "Epicron 830S" manufactured by Dainippon Ink and Chemicals, Inc. Epoxy resin 3: Phenol novolac type epoxy resin "Epicron HP-4710" manufactured by Dainippon Ink and Chemicals, Inc. Epoxy resin 4: Modified bisphenol A type epoxy resin "Epicron EXA-4850-150" manufactured by Dainippon Ink and Chemicals, Inc. Cyanate resin: Phenol novolac type cyanate resin "PT-30" manufactured by Lonza Elastomer: Epoxidized polybutadiene JP-200 manufactured by Nippon Soda Co., Ltd. Coupling agent: Epoxy silane coupling agent (γ-glycidoxypropyltrimethoxysilane) "A-187" manufactured by Momentive Corporation Leveling agent; polyacrylate compound "BYK-361N" manufactured by BYK-Chemie Curing accelerator: TBZ (Shikoku Kasei Co., Ltd., 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole)

[0101] 2) The obtained thermosetting resin composition was used to carry out the following evaluations and measurements. Linear expansion coefficient α1 The thermal expansion coefficient was measured using a TMA (thermal mechanical analysis) device (Q400, manufactured by TA Instruments) by preparing a 4 mm × 20 mm test piece and measuring the linear expansion coefficient (CTE) α1 during the heating process from 50 to 150°C in the second cycle under conditions of a temperature range of 30 to 300°C, 10°C / min, and a load of 5 g. The test specimens were prepared according to the following procedure. The above thermosetting resin composition molded to about 100 μm was press-cured under conditions of 200° C. / 1 hr, and then cut to a predetermined size to prepare a test piece.

[0102] Complex dynamic viscosity A dynamic viscoelasticity test was performed on a resin film made of the thermosetting resin composition in a B-stage state to measure the complex dynamic viscosity in a measurement range of 50 to 200°C, a heating rate of 3°C / min, and a frequency of 62.83 rad / sec, and the minimum value η was determined.

[0103] Elasticity modulus Using a dynamic viscoelasticity device, the storage modulus (GPa) was calculated according to JISC-6481 (DMA method) at 30° C. and 250° C. Test pieces for measurement were prepared by press-curing the above-mentioned thermosetting resin composition molded to about 100 μm at 200° C. / 1 hr.

[0104] ·warp A copper frame was prepared by etching a 140 μm thick copper plate with a pattern of 100 μm copper posts. The above thermosetting resin composition was laminated on the copper frame to a thickness of 100 μm, and cured at 200° C. for 60 minutes to prepare a laminate. The warpage of the obtained laminate was evaluated according to the following evaluation criteria, with a sample size of 200 mm×80 mm placed on a flat surface with the resin surface facing up, and the height from the flat surface was taken as the warpage. ◎: No warping was observed. ○: Warpage was less than 2 mm. ×: Warpage was 2mm or more.

[0105] - Electrode pad sinking The above thermosetting resin composition was cured at 200° C. for 60 minutes to obtain a cured product having a thickness of 100 μm. A copper pad was formed on the obtained cured product, and a bonding device (UTC-5000 NeoCu (manufactured by Shinkawa Co., Ltd.)) was used to strike the copper pad from above (load 200 g, ultrasonic wave 300, temperature 170° C.), and the sinking of the copper pad was evaluated according to the following evaluation criteria. ◎:No sinking. ○: Sinking of about 5 μm. ×: Cracks in the resin.

[0106] [Table 1] [Explanation of symbols]

[0107] 10 metal plate 11 Circuit Pattern 12 Lead frame 20 Thermosetting resin composition 30 Electrode Pads 31 Semiconductor elements 41 Bonding Wire 42 Sealing body 100 Semiconductor device

Claims

1. A thermosetting resin composition comprising an epoxy resin and a benzoxazine resin, the linear expansion coefficient α1 of the thermosetting resin composition measured using a thermomechanical analyzer during a temperature rise process from 50° C. to 150° C. is 8 ppm / ° C. or more and 15 ppm / ° C. or less; A thermosetting resin composition (excluding thermosetting resin compositions containing bismaleimide resins) for use in copper foil and / or copper-based alloy foil, wherein η is the minimum value of complex dynamic viscosity in a dynamic viscoelasticity test of a resin film made of the thermosetting resin composition in a B-stage state, the minimum value being η within a measurement range of 50 to 200° C., a heating rate of 3° C. / min, and a frequency of 62.83 rad / sec, and the value is η=100 Pa·s or more and 5000 Pa·s or less.

2. The thermosetting resin composition according to claim 1, A thermosetting resin composition, wherein the content of the benzoxazine resin is 8% by mass or more and 30% by mass or less, when the entire thermosetting resin composition is taken as 100% by mass.

3. The thermosetting resin composition according to claim 1 or 2, The thermosetting resin composition further comprises an inorganic filler.

4. The thermosetting resin composition according to claim 3, The thermosetting resin composition, wherein the inorganic filler comprises silica.

5. The thermosetting resin composition according to claim 3 or 4, A thermosetting resin composition, wherein the content of the inorganic filler is 60% by mass or more and 95% by mass or less, based on the total mass of the thermosetting resin composition.

6. The thermosetting resin composition according to any one of claims 1 to 5, The thermosetting resin composition further comprises a cyanate resin.

7. A resin film comprising the thermosetting resin composition according to claim 1 .

8. A carrier substrate; A resin film with a carrier, comprising: a resin film formed on the carrier base material, the resin film being made of the thermosetting resin composition according to claim 1 .

9. A prepreg obtained by impregnating a fiber substrate with the thermosetting resin composition according to any one of claims 1 to 6.

10. A semiconductor element provided on a substrate; a bonding wire connected to the semiconductor element; an electrode pad electrically connected to the bonding wire; Equipped with A semiconductor device, comprising: the electrode pads disposed on a cured product of the thermosetting resin composition according to claim 1 .

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