Thermosetting resin composition, prepreg, resin film, laminate, laminate plate, printed wiring board, and semiconductor package

Abstract

Provided is a thermosetting resin composition capable of suppressing the occurrence of molding defects in an insulating layer. The present invention also provides a prepreg, a resin film, a laminate, a laminate plate, a printed wiring board, and a semiconductor package that are obtained using the thermosetting resin composition. Specifically, the thermosetting resin composition contains (A) a maleimide compound and (B) an inorganic filler having a volume-average particle size of 2.5 μm or more.

Description

Thermosetting resin composition, prepreg, resin film, laminate, laminated board, printed wiring board, and semiconductor package

[0001] The present disclosure relates to a thermosetting resin composition, a prepreg, a resin film, a laminate, a laminated board, a printed wiring board, and a semiconductor package.

[0002] In recent years, the demand for high-performance and large-sized semiconductor package substrates has been increasing. For the enlargement of semiconductor package substrates, instead of organic materials (for example, prepregs containing glass cloth and resin compositions), which are existing substrate materials, it has been proposed to use a glass plate as a core substrate. However, since organic materials have important properties such as high adhesiveness to conductor layers, there is also a need to develop a technology for enlarging semiconductor package substrates while still using organic materials as core substrates. Another problem is that large semiconductor package substrates are prone to warping. When an organic material is used as the core substrate of a large-sized semiconductor package, the organic material has less rigidity than a glass plate, so there is a tendency for the semiconductor package to warp more easily than when a glass plate is used. As a method for increasing the rigidity of the organic material, it is conceivable to contain an inorganic filler. As a resin composition containing an inorganic filler, for example, the resin composition described in Patent Document 1 is known.

[0003] Japanese Patent Application Laid-Open No. 2024-119896

[0004] In the examples of Patent Document 1, silica having an average particle diameter of 0.5 μm is used as the inorganic filler. However, as a result of intensive studies by the present inventors, in the case of a resin composition containing an inorganic filler with a small average particle diameter, when the blending amount of the inorganic filler is increased to increase the rigidity (elastic modulus), it has been found that the tendency for molding defects to occur in the formed insulating layer increases. Since the molding defects can cause deterioration of insulation reliability, it is required to suppress the occurrence of molding defects.

[0005] In view of the current situation, this disclosure aims to provide a thermosetting resin composition that can suppress the occurrence of molding defects in the insulating layer, and to provide a prepreg, resin film, laminate, laminate board, printed circuit board, and semiconductor package that can be obtained using the thermosetting resin composition.

[0006] As a result of diligent research, the inventors have found that the thermosetting resin composition of this disclosure can achieve the above objective.

[0007] This disclosure includes the following embodiments [1] to

[13] : [1] A thermosetting resin composition comprising (A) a maleimide compound and (B) an inorganic filler with a volume average particle diameter of 2.5 μm or more. [2] The thermosetting resin composition according to [1], wherein the nitrogen atoms of the N-substituted maleimide group of component (A) are bonded to each other via a linking group containing an aromatic ring. [3] The thermosetting resin composition according to [1] or [2], wherein the content of component (B) is 55% by volume or more with respect to the total amount of solids. [4] The thermosetting resin composition according to any one of [1] to [3] above, wherein component (B) is one or more selected from the group consisting of silica, alumina, titanium oxide, mica, beryllium, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, molybdate compounds, talc, aluminum borate, and silicon carbide. [5] The thermosetting resin composition according to any one of [1] to [4] above, further containing (C) a thermosetting resin (excluding component (A) above). [6] The thermosetting resin composition according to any one of [1] to [5] above, for use as an interlayer insulating layer of a printed circuit board. [7] A prepreg containing the thermosetting resin composition according to any one of [1] to [6] above or a semi-cured product of the thermosetting resin composition. [8] A resin film containing the thermosetting resin composition described in any of [1] to [6] above or a semi-cured product of the thermosetting resin composition. [9] A laminate in which the resin film described in [8] above or its cured product, a support layer, and the resin film described in [8] above or its cured product are laminated in this order.

[10] A laminate having a cured product of the thermosetting resin composition described in any of [1] to [6] above and a metal foil.

[11] A laminate having a cured product of the prepreg described in [7] above, a cured product of the resin film described in [8] above or a cured product of the laminate described in [9] above and a metal foil.

[12] A printed circuit board having a cured product of the thermosetting resin composition described in any of [1] to [6] above, a cured product of the prepreg described in [7] above, a cured product of the resin film described in [8] above or a cured product of the laminate described in [9] above.

[13] A semiconductor package having a printed circuit board according to claim 12 and a semiconductor element.

[0008] This disclosure provides a thermosetting resin composition that can suppress the occurrence of molding defects in the insulating layer, and also provides a prepreg, resin film, laminate, laminate board, printed circuit board, and semiconductor package obtained using the thermosetting resin composition.

[0009] This is a schematic cross-sectional view of the prepreg of this embodiment. This is a digital camera image of the insulating layer surface corresponding to evaluation "A" of the insulating layer of the resin plate in the example or comparative example. This is a digital camera image of the insulating layer surface corresponding to evaluation "A" of the insulating layer of the copper-clad laminate in the example or comparative example. This is a digital camera image of the insulating layer surface corresponding to evaluation "B" of the insulating layer of the resin plate in the example or comparative example. This is a digital camera image of the insulating layer surface corresponding to evaluation "B" of the insulating layer of the copper-clad laminate in the example or comparative example. This is a digital camera image of the insulating layer surface corresponding to evaluation "C" of the insulating layer of the resin plate in the example or comparative example. This is a digital camera image of the insulating layer surface corresponding to evaluation "C" of the insulating layer of the copper-clad laminate in the example or comparative example.

[0010] In the numerical ranges described in this disclosure, the upper or lower limits of the numerical range may be replaced with the values ​​shown in the examples. Furthermore, the lower and upper limits of a numerical range may be arbitrarily combined with the lower or upper limits of other numerical ranges. In the notation "AA to BB" for a numerical range, the numbers AA and BB at both ends are included in the range as the lower and upper limits, respectively. In this disclosure, for example, "10 or more" means 10 and numbers greater than 10, and this applies even if the numbers are different. Similarly, for example, "10 or less" means 10 and numbers less than 10, and this applies even if the numbers are different. Furthermore, unless otherwise specified, each component and material exemplified in this disclosure may be used alone or in combination of two or more. In this disclosure, if there are multiple substances corresponding to each component in the resin composition, unless otherwise specified, the content of each component in the resin composition means the total amount of such multiple substances present in the resin composition.

[0011] In this disclosure, "resin components" refers to all components of the resin composition that constitute the solid content, excluding inorganic compounds such as inorganic fillers described later. In this disclosure, "solid content" refers to components other than organic solvents described later, and components that are liquid at 25°C are also considered to be solid content. The expression "contains XX" as described in this disclosure means that XX may be contained in a reacted state if XX is reactable, or it may simply mean that XX is contained. Any combination of the information described in this disclosure is also included in this disclosure and these embodiments.

[0012] [Thermosetting Resin Composition] The thermosetting resin composition of this embodiment is a thermosetting resin composition containing (A) a maleimide compound and (B) an inorganic filler with a volume average particle diameter of 2.5 μm or more. The components contained in the thermosetting resin composition of this embodiment will be described in detail below.

[0013] ((A) Maleimide Compound) The thermosetting resin composition of this embodiment contains component (A), which provides excellent solder heat resistance and moldability, and is therefore useful, for example, as an interlayer insulating layer for printed circuit boards. The maleimide compound preferably contains at least one selected from the group consisting of maleimide compounds and derivatives thereof having one or more (preferably two or more) N-substituted maleimide groups. Maleimide compounds having one or more N-substituted maleimide groups are not particularly limited, but preferably aromatic maleimide compounds having one N-substituted maleimide group bonded to an aromatic ring, such as N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-benzylmaleimide; 4,4'-diphenylmethanebismaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, Examples include aromatic bismaleimide compounds having two N-substituted maleimide groups preferably bonded to an aromatic ring, such as m-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and indan ring-containing aromatic bismaleimide; aromatic polymaleimide compounds having three or more N-substituted maleimide groups preferably bonded to an aromatic ring, such as polyphenylmethanemaleimide and biphenylaralkyl-type maleimide; and aliphatic maleimide compounds having N-substituted maleimide groups bonded to an aliphatic hydrocarbon group, such as N-dodecylmaleimide, N-isopropylmaleimide, and N-cyclohexylmaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, and pyrophosphate binder-type long-chain alkylbismaleimide.Among these, from the viewpoint of compatibility with other resin components, copper foil peel strength, solder heat resistance, low thermal expansion, and mechanical properties, aromatic bismaleimide compounds having two N-substituted maleimide groups bonded to the aromatic ring, preferably aromatic polymaleimide compounds having three or more N-substituted maleimide groups bonded to the aromatic ring, more preferably 4,4'-diphenylmethanebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and polyphenylmethanemaleimide, and even more preferably 4,4'-diphenylmethanebismaleimide. Furthermore, in the maleimide compounds, it is preferable that the nitrogen atom of the maleimide group is bonded to the aromatic ring in all cases of "preferably one N-substituted maleimide group bonded to the aromatic ring," "preferably two N-substituted maleimide groups bonded to the aromatic ring," and "preferably three or more N-substituted maleimide groups bonded to the aromatic ring." In the maleimide compound, it is preferable that the nitrogen atoms of the N-substituted maleimide group are bonded to each other via a linking group, and more preferably that the nitrogen atoms of the N-substituted maleimide group are bonded to each other via a linking group containing an aromatic ring.

[0014] Examples of maleimide compound derivatives include addition reaction products of a maleimide compound having one or more (preferably two or more) N-substituted maleimide groups and an amine compound. Examples of the amine compound include monoamine compounds and diamine compounds. The amine compound may be used alone or in combination of two or more. Examples of the monoamine compound include monoamine compounds having acidic substituents such as o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline. The monoamine compound may be used alone or in combination of two or more. The diamine compounds include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 2,2'-bis(4,4'-diaminodiphenyl)propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylethane, 3,3'-diethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenylthioe Examples include aromatic diamine compounds in which an amino group is bonded to an aromatic hydrocarbon group, such as 3,3'-dihydroxy-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetrachloro-4,4'-diaminodiphenylmethane, and 2,2',6,6'-tetrabromo-4,4'-diaminodiphenylmethane; siloxanediamines; etc. Diamine compounds may be used individually or in combination of two or more. The siloxanediamine is a silicone compound having a primary amino group at its terminus.

[0015] A preferred embodiment of the maleimide compound derivative is a so-called siloxane-modified maleimide compound, which is an addition reaction product of a maleimide compound having one or more (preferably two or more) N-substituted maleimide groups with a siloxanediamine. Preferably, the siloxane-modified maleimide compound is an addition product of an aromatic bismaleimide compound having two N-substituted maleimide groups bonded to an aromatic ring and a siloxanediamine; more preferably, an addition product of 4,4'-diphenylmethanebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, or an indan ring-containing aromatic bismaleimide and a siloxanediamine; even more preferably, an addition product of 4,4'-diphenylmethanebismaleimide and a siloxanediamine, or an addition product of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane and a siloxanediamine; and particularly preferably, an addition product of 4,4'-diphenylmethanebismaleimide and a siloxanediamine. The weight-average molecular weight (Mw) of the siloxane-modified maleimide compound is not particularly limited, but may be 400 to 10,000, 1,000 to 5,000, or 1,500 to 4,000.

[0016] (Content of component (A)) The content of component (A) in the thermosetting resin composition of this embodiment is not particularly limited, but from the viewpoint of solder heat resistance and moldability, it is preferably 10 to 90 parts by mass, more preferably 20 to 85 parts by mass, even more preferably 30 to 80 parts by mass, and particularly preferably 45 to 75 parts by mass, per 100 parts by mass of the resin component in the thermosetting resin composition of this embodiment. When the content of component (A) is above the lower limit, solder heat resistance and moldability tend to improve, and when it is below the upper limit, the decrease in low thermal expansion tends to be suppressed.

[0017] ((B) Inorganic filler with a volume average particle diameter of 2.5 μm or more) The thermosetting resin composition of this embodiment, by containing component (B), exhibits excellent low thermal expansion, heat resistance, and flame retardancy. Furthermore, because the volume average particle diameter of component (B) is 2.5 μm or more, even if the content of component (B) is high, it is possible to suppress the occurrence of molding defects in the insulating layer. The content of component (B) will be described later. From the viewpoint of suppressing the occurrence of molding defects in the insulating layer, the volume average particle diameter of component (B) is preferably 3.0 μm or more, may be 3.5 μm or more, may be 4.0 μm or more, may be 5.0 μm or more, may be 7.0 μm or more, may be 8.0 μm or more, or may be 9.0 μm or more. There is no particular upper limit to the volume-average particle diameter of component (B), but from the viewpoint of insulation reliability, it is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, and particularly preferably the volume-average particle diameter is 50% or less of the thickness of the varnish when applied. In other words, the volume-average particle diameter of component (B) may be 2.5 to 50 μm, and the preferred values ​​for the lower and upper limits of this numerical range are as described above. Here, the volume-average particle diameter is the particle diameter at the point corresponding to 50% of the volume when the cumulative frequency distribution curve by particle diameter is obtained with the total volume of the particles set to 100%. In this disclosure, the volume-average particle diameter is the value measured with a particle diameter distribution measuring device using the laser diffraction scattering method, and more specifically, the value measured by the method described in the examples.

[0018] Component (B) is not particularly limited, but examples include silica, alumina, titanium oxide, mica, beryllium, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (such as calcined clay), molybdate compounds (such as zinc molybdate), talc, aluminum borate, silicon carbide, etc. Component (B) may be used alone or in combination of two or more. Among these, silica, alumina, mica, and talc are preferred from the viewpoint of low thermal expansion, heat resistance, and flame retardancy, silica and alumina are more preferred, and silica is even more preferred. Examples of silica include crushed silica, fumed silica, and fused silica (fused spherical silica).

[0019] (Content of component (B)) The content of component (B) in the thermosetting resin composition of this embodiment is not particularly limited, but is preferably 1 to 80 volume%, more preferably 5 to 75 volume%, even more preferably 10 to 75 volume%, even more preferably 30 to 75 volume%, particularly preferably 50 to 75 volume%, and most preferably 60 to 75 volume%, relative to the total amount of solids in the thermosetting resin composition. When the content of component (B) is above the lower limit, it tends to be excellent in low thermal expansion, heat resistance and flame retardancy. When the content of component (B) is below the upper limit, it tends to be good in moldability and insulation reliability. As mentioned above, in this embodiment, even if the content of component (B) is high, it is possible to suppress the occurrence of molding defects in the insulating layer, so it is possible to set the content of component (B) to 55 volume% or more relative to the total amount of solids in the thermosetting resin composition. When the content of component (B) is increased, the content of component (B) may be 60% by volume or more relative to the total amount of solids in the thermosetting resin composition, preferably 60 to 80% by volume, more preferably 63 to 78% by volume, even more preferably 63 to 75% by volume, particularly preferably 63 to 73% by volume, and most preferably 65 to 70% by volume.

[0020] Furthermore, when using component (B), a coupling agent may be used in combination as needed to improve the dispersibility of component (B) and the adhesion between component (B) and the organic components in the thermosetting resin composition. The coupling agent is not particularly limited, and for example, a silane coupling agent or a titanate coupling agent may be appropriately selected and used. One type of coupling agent may be used alone, or two or more types may be used in combination. The amount of coupling agent used is also not particularly limited. When using a coupling agent, a so-called integral blending method may be used, in which the coupling agent is added after the component (B) has been blended into the thermosetting resin composition. However, it is preferable to use an inorganic filler in which the coupling agent has been pre-treated on the inorganic filler surface by dry or wet methods. By adopting this method, the characteristics of component (B) can be expressed more effectively.

[0021] In this embodiment, when component (B) is used, in order to improve the dispersibility of component (B) in the thermosetting resin composition, it may be used as a slurry in which component (B) is pre-dispersed in an organic solvent, if necessary. Examples of organic solvents include those described later.

[0022] ((C) Thermosetting resin) The thermosetting resin composition of this embodiment may or may not contain (C) thermosetting resin (except for component (A) above). Component (C) includes one or more thermosetting resins selected from the group consisting of epoxy resins, phenolic resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins (such as melamine resins), bismaleimidotriazine resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, and silicone resins. Component (C) is preferably one or more selected from the group consisting of epoxy resins, phenolic resins, cyanate resins, isocyanate resins, amino resins, unsaturated polyester resins, and silicone resins; more preferably one or more selected from the group consisting of epoxy resins, phenolic resins, cyanate resins, and isocyanate resins; even more preferably one or more selected from the group consisting of epoxy resins, phenolic resins, and cyanate resins; and particularly preferably an epoxy resin.

[0023] The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. Here, epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred. The epoxy resins mentioned above can be further classified into various types of epoxy resins depending on the difference in their main skeleton. Within each of these types of epoxy resins, they can be further classified into bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, and bisphenol S type epoxy resin; alicyclic epoxy resins such as dicyclopentadiene type epoxy resin; aliphatic chain epoxy resins; novolac-type epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, phenol aralkyl novolac type epoxy resin, and biphenyl aralkyl novolac type epoxy resin; stilbene type epoxy resin; naphthalene skeleton-containing epoxy resins such as naphthalene type epoxy resin, naphthol novolac type epoxy resin, and naphthol aralkyl type epoxy resin; biphenyl type epoxy resin; xylylene type epoxy resin; and dihydroanthracene type epoxy resin.

[0024] The aforementioned component (C) is not particularly limited, but may contain an epoxy resin having a viscosity of 30 Pa·s or less at 150°C, or component (C) may be an epoxy resin having a viscosity of 30 Pa·s or less at 150°C. In this disclosure, viscosity is a value based on a viscosity measurement method using an isothermal titration calorimeter (ICT). The epoxy resin having a viscosity of 30 Pa·s or less at 150°C is preferably 25 Pa·s or less, more preferably 10 Pa·s or less, and even more preferably 5 Pa·s or less. The lower limit of viscosity at 150°C is not particularly limited, but may be 5 mPa·s or more, 20 mPa·s or more, 50 mPa·s or more, or 100 mPa·s or more. In other words, the epoxy resin may have a viscosity of 5 mPa·s to 30 Pa·s at 150°C. By including an epoxy resin in component (C) whose viscosity at 150°C is within the aforementioned range, the viscosity of the thermosetting resin composition can be reduced even if component (A) has high viscosity, and the moldability tends to be good, thus making it easier to suppress molding defects in the insulating layer.

[0025] As epoxy resins with a viscosity of 30 Pa·s or less at 150°C, non-novolac epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resins having a butadiene structure are preferred, bisphenol A type epoxy resin and naphthalene type epoxy resin are more preferred, and bisphenol A type epoxy resin is even more preferred. Epoxy resins with a viscosity of 30 Pa·s or less at 150°C may be used individually or in combination of two or more types. Commercially available epoxy resins include: "HP4032," "HP4032D," and "HP4032SS" (all naphthalene-type epoxy resins) from DIC Corporation; "jER828US," "jER828EL," "jER828EL," "jER825," and "jER828EL" (all bisphenol A-type epoxy resins) from Mitsubishi Chemical Corporation; and "jER807" and "jER1750" (both bisphenol A-type epoxy resins) from Mitsubishi Chemical Corporation. Examples include: EP-4088S and EP-4040 (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; PB-3600 manufactured by Daicel Corporation; and JP-100 and JP-200 manufactured by Nippon Soda Co., Ltd. (all epoxy resins having a butadiene structure).

[0026] The weight-average molecular weight of the epoxy resin may be 200 to 3,000, 250 to 2,000, 300 to 1,800, or 400 to 1,500. If the weight-average molecular weight of the epoxy resin is above the lower limit, it tends to have excellent solder heat resistance, and if it is below the upper limit, it tends to exhibit low elasticity and flexibility. From the viewpoint of compatibility, the epoxy equivalent of the epoxy resin may be 150 to 500 g / eq, 200 to 450 g / eq, or 250 to 350 g / eq. The epoxy equivalent can be measured according to the method specified in JIS K7236 (2009).

[0027] (Content of (C) Thermosetting Resin) When the thermosetting resin composition of this embodiment contains component (C), the content of component (C) is not particularly limited, but is preferably 10 to 90 parts by mass, more preferably 15 to 80 parts by mass, even more preferably 20 to 70 parts by mass, and particularly preferably 25 to 55 parts by mass, per 100 parts by mass of the resin component in the thermosetting resin composition. When the content of component (C) is above the lower limit, the solder heat resistance and moldability tend to be good. When the content of component (C) is below the upper limit, the low thermal expansion tend to be good.

[0028] ((D) Curing Accelerator) The thermosetting resin composition of this embodiment may contain a (D) curing accelerator from the viewpoint of promoting the curing reaction. Examples of component (D) include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, organometallic salts, acidic catalysts, organic peroxides, etc. In this disclosure, imidazole-based curing accelerators are not classified as amine-based curing accelerators. Component (D) may be used alone or in combination of two or more. The thermosetting resin composition of this embodiment preferably contains an imidazole-based curing accelerator and a phosphorus-based curing accelerator as component (D), and may contain an imidazole-based curing accelerator or a phosphorus-based curing accelerator.

[0029] Examples of the amine-based curing accelerator include amine compounds having primary to tertiary amino groups, such as triethylamine, 4-aminopyridine, tributylamine, and dicyandiamide; and quaternary ammonium compounds. Examples of the imidazole-based curing accelerator include imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, and isocyanate-masquimidazole (for example, the addition product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole). Examples of the phosphorus-based curing accelerator include tertiary phosphines such as triphenylphosphine; and quaternary phosphonium compounds such as the addition product of p-benzoquinone with tri-n-butylphosphine. Examples of the organometallic salts include carboxylates of manganese, cobalt, zinc, etc. Examples of the acidic catalyst include p-toluenesulfonic acid. Examples of the aforementioned organic peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3,2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-di(t-butylperoxy)diisopropylbenzene.

[0030] (Content of curing accelerator (D)) When the thermosetting resin composition of this embodiment contains component (D), the content of component (D) is not particularly limited, but is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass, even more preferably 0.1 to 2.0 parts by mass, and particularly preferably 0.3 to 1.5 parts by mass, per 100 parts by mass of the resin component in the thermosetting resin composition. When the content of component (D) is within the above range, better heat resistance, storage stability, and moldability tend to be obtained.

[0031] (Other Components) The thermosetting resin composition of this embodiment may or may not contain one or more other components selected from the group consisting of flame retardants, flame retardant aids, antioxidants, adhesion improvers, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants. It may also contain or may not contain any other components. When the thermosetting resin composition of this embodiment contains these other components (flame retardants, flame retardant aids, antioxidants, adhesion improvers, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and other components), the amount of each is not particularly limited, but may be, for example, 0.01 parts by mass or more, 10 parts by mass or less, 5 parts by mass or less, 1 part by mass or less, or not contained at all, per 100 parts by mass of the resin component in the thermosetting resin composition.

[0032] The thermosetting resin composition of this embodiment preferably has a total amount of components (A) to (B) above [however, if the thermosetting resin composition contains at least one of components (C) and (D), the total amount including those components] that is greater than 50% by mass (including 100% by mass), more preferably 70% by mass or more (including 100% by mass), even more preferably 80% by mass or more (including 100% by mass), particularly preferably 90% by mass or more (including 100% by mass), and may also be 100% by mass.

[0033] (Organic solvent) The thermosetting resin composition of this embodiment may be a so-called "varnish" containing an organic solvent, from the viewpoint of facilitating handling and facilitating the production of prepregs or resin films described later. The organic solvent is not particularly limited, but examples include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone. From the viewpoint of solubility, ketone-based solvents and alcohol-based solvents are preferred, methyl ethyl ketone and propylene glycol monomethyl ether are more preferred, and propylene glycol monomethyl ether is even more preferred. One organic solvent may be used alone, or two or more may be used in combination.

[0034] When the thermosetting resin composition of this embodiment is used as a varnish, the solid content concentration is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 55 to 75% by mass. When the solid content concentration of the thermosetting resin composition is within the above range, the handling of the thermosetting resin composition becomes easier, the impregnation into the substrate and the appearance of the manufactured prepreg become good, and the coating properties when made into a resin film also become good.

[0035] The thermosetting resin composition of this embodiment can be produced by mixing components (A) to (B) and any other components that may be used as needed, using a known method. In this case, each component may be dissolved or dispersed in the organic solvent while stirring. The mixing order, temperature, time, and other conditions are not particularly limited and can be set arbitrarily.

[0036] [Prepreg] The prepreg of this embodiment is a prepreg containing the thermosetting resin composition of this embodiment or a semi-cured product of the thermosetting resin composition. The prepreg of this embodiment contains, for example, the thermosetting resin composition of this embodiment or a semi-cured product of the thermosetting resin composition and glass cloth. The prepreg is formed using a resin film, described later, formed from the thermosetting resin composition of this embodiment, and glass cloth. For example, it can be obtained by impregnating a glass cloth with a resin film, described later, formed from the thermosetting resin composition of this embodiment, for example, by lamination. The thermosetting resin composition in the prepreg obtained after lamination is B-staged. Here, in this disclosure, B-staged means being in the B-stage state as defined in JIS K6900 (1994). There are no particular restrictions on the lamination conditions, and roll lamination may be performed under normal pressure or vacuum lamination may be performed, but vacuum lamination is preferred. The conditions for vacuum lamination are not particularly limited, but the heating temperature is preferably 50 to 170°C, more preferably 110 to 160°C, the pressurizing time is preferably 10 to 120 seconds, more preferably 20 to 80 seconds, and the bonding pressure is preferably 0.05 to 1.5 MPa, more preferably 0.1 to 1.2 MPa.

[0037] The material of the glass cloth is not particularly limited, but examples include E glass, D glass, S glass, Q glass (quartz glass), etc. The thickness of the glass cloth is not particularly limited and may be 1 to 200 μm, 3 to 150 μm, 5 to 120 μm, or 5 to 100 μm.

[0038] The prepreg of this embodiment uses a thermosetting resin containing "(B) inorganic filler with a large particle size, having a volume average particle diameter of 2.5 μm or more," so it is preferable that the thickness of the thermosetting resin composition layer that protrudes onto the glass cloth is large. As shown in Figure 1, the thickness of the thermosetting resin composition layer that protrudes onto the glass cloth corresponds to the value obtained by multiplying the difference between the thickness of the prepreg and the thickness of the glass cloth by 1 / 2. If the prepreg is further heated and cured, the thickness can also be measured from its cross-section. The thickness of the thermosetting resin composition layer that protrudes onto the glass cloth is preferably at least twice the volume average particle diameter of component (B) on both sides, and specifically, preferably 15 to 90 μm, more preferably 20 to 80 μm, even more preferably 25 to 70 μm, and particularly preferably 25 to 60 μm. Conventionally, in prepregs for interlayer insulating layers of printed circuit boards, the thickness of the thermosetting resin composition layer overflowing onto the glass cloth has not been set to such a large size from the viewpoint of suppressing thickness variations caused by the flow of resin components. However, in the prepreg of this embodiment, by setting the thickness of the thermosetting resin composition layer overflowing onto the glass cloth to the above range, it becomes possible to increase the amount of component (B), which has a large particle size, in order to further increase rigidity (elastic modulus). Even in this case, molding defects tend to occur less frequently in the insulating layer that is formed. Here, the thickness of the glass cloth in the prepreg is the average value of five points: the four corners of the glass cloth in the prepreg (however, 10 mm from the edge of the glass cloth) and the center. The thickness of the glass cloth can be measured after removing the thermosetting resin composition layer by etching or the like, or the thickness of the glass cloth to be used can be measured in advance before manufacturing the prepreg. Furthermore, the thickness of the thermosetting resin composition layer extending beyond the glass cloth refers to the average value of five points: the four corners of the prepreg (10 mm from the edge of the prepreg) and the center. A micrometer can be used to measure these thicknesses.

[0039] [Resin Film] The resin film of this embodiment is a resin film containing the thermosetting resin composition of this embodiment or a semi-cured product of the thermosetting resin composition. The resin film of this embodiment can be manufactured, for example, by applying a thermosetting resin composition containing an organic solvent, i.e., a varnish, to a support, heating and drying it, and semi-curing it (B-stage) as needed. The thickness of the resin film is preferably 10 to 80 μm, more preferably 15 to 70 μm, even more preferably 20 to 60 μm, and particularly preferably 40 to 60 μm, from the viewpoint of enabling high filling of component (B). Examples of the support include plastic film, metal foil, and release paper. The drying temperature and drying time can be appropriately determined according to the amount of organic solvent used and the boiling point of the organic solvent used, but the resin film can be suitably formed by drying at 50 to 200°C for about 1 to 10 minutes.

[0040] [Laminate] The laminate of this embodiment is a laminate in which the resin film or cured product thereof of this embodiment, a support layer, and the resin film or cured product thereof of this embodiment are laminated in this order. The support layer may be a glass plate, a resin film (except for the resin film of this embodiment), etc. The material of the glass plate is not particularly limited, but may be E glass, D glass, S glass, Q glass (quartz glass), etc. The resin film is not particularly limited, but may be a polyolefin film such as polyethylene, polypropylene, or polyvinyl chloride; a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate; a polycarbonate film, a polyimide film, etc.

[0041] There are no particular restrictions on the thickness of the support layer, but it may be 1 to 500 μm, 3 to 400 μm, 5 to 300 μm, or 5 to 200 μm.

[0042] The laminate of this embodiment is not particularly limited, but it is preferable that it does not contain a fibrous base material such as glass cloth. Even if it does contain a fibrous base material such as glass cloth, its content is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 1% by mass or less, and most preferably 0.5% by mass or less, based on the total mass of the laminate.

[0043] [Laminate] The laminate of this embodiment is a laminate having a cured product of the thermosetting resin composition of this embodiment, a cured product of the prepreg of this embodiment, a cured product of the resin film of this embodiment, or a cured product of the laminate of this embodiment, and a metal foil. Here, the cured product of the laminate of this embodiment corresponds to "a laminate in which the cured product of the resin film of this embodiment, a support layer, and the cured product of the resin film of this embodiment are laminated in this order." The laminate of this embodiment can be manufactured, for example, by placing a metal foil on one or both sides of one prepreg or laminate of this embodiment (here, a laminate in which the resin film of this embodiment, a support layer, and the resin film of this embodiment are laminated in this order), or by placing a metal foil on one or both sides of a laminate obtained by stacking two or more (preferably 2 to 30 sheets, more preferably 2 to 20 sheets, and even more preferably 2 to 10 sheets) of the prepreg or laminate of this embodiment (here, a laminate in which the resin film of this embodiment, a support layer, and the resin film of this embodiment are laminated in this order), and then heating and pressing it. In the laminate obtained by this manufacturing method, the thermosetting resin composition in the prepreg of this embodiment or the resin film in the laminate of this embodiment is C-staged. In this disclosure, C-staged means being in the state of C-stage as defined in JIS K6900 (1994). Laminates having metal foil are sometimes called metal-clad laminates. The metal of the metal foil is not particularly limited, but from the viewpoint of conductivity, it may be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing one or more of these metal elements, with copper and aluminum being preferred, and copper being more preferred. The method of heat-pressure molding is not particularly limited, but for example, it can be carried out under conditions of a temperature of 100 to 300°C, a pressure of 0.2 to 10 MPa, and a time of 0.1 to 5 hours. Furthermore, the heat-pressure molding can be carried out by using a vacuum press or the like to maintain a vacuum state for 0.5 to 5 hours.

[0044] [Printed Wiring Board] The printed wiring board of the present embodiment has one or more selected from the group consisting of a cured product of the thermosetting resin composition of the present embodiment, a cured product of the prepreg of the present embodiment, a cured product of the resin film of the present embodiment, a cured product of the laminate of the present embodiment, and the laminate plate of the present embodiment. The printed wiring board of the present embodiment can be manufactured by performing circuit formation processing such as drilling, metal plating, and etching of metal foil by a known method using one or more selected from the group consisting of the prepreg of the present embodiment, the resin film of the present embodiment, and the laminate plate of the present embodiment. Further, a multilayer printed wiring board can also be manufactured by performing multilayer bonding processing as necessary. In the printed wiring board of the present embodiment, the prepreg and the resin film of the present embodiment are in a C-stage state. In this way, the thermosetting resin composition or prepreg of the present embodiment serves as an interlayer insulating layer of the printed wiring board.

[0045] [Semiconductor Package] The semiconductor package of the present embodiment is a semiconductor package having the printed wiring board of the present embodiment and a semiconductor element. The semiconductor package of the present embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position on the printed wiring board of the present embodiment and sealing the semiconductor element with a sealing resin or the like.

[0046] Although the preferred embodiments have been described above, these are examples for the explanation of the present disclosure, and the scope of the present disclosure is not intended to be limited only to these embodiments. The present disclosure includes various aspects different from the above embodiments without departing from the gist thereof.

[0047] Hereinafter, the present embodiment will be specifically described with reference to examples. However, the present embodiment is not limited to the following examples.

[0048] Production Example 1 (Production of a Maleimide Compound Derivative (Maleimide Compound 1)) In a 2 L volume reaction vessel that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with reflux condenser, 358.0 g of 4,4'-diphenylmethanebismaleimide, 54.5 g of p-aminophenol, and 412.50 g of propylene glycol monomethyl ether were mixed (maleimide group equivalent) / (-NH ２ After mixing in a ratio such that the equivalent amount (based on the number of groups) = 4.0, the mixture was reacted under reflux for 5 hours to obtain a solution of a derivative of the maleimide compound (maleimide compound 1).

[0049] [Examples 1-5, Comparative Examples 1-2] (1. Preparation of Varnish) A thermosetting resin composition (varnish) with a solid content of 70% by mass was prepared by mixing and stirring each component listed in Table 1 with propylene glycol monomethyl ether at room temperature according to the proportions listed in Table 1. (2. Preparation of Resin Film) The varnish thus obtained was applied to a PET film (manufactured by Toray Industries, Inc., thickness: 50 μm, product name: S10) using a comma coater so that the thickness after drying was 55 μm. Then, a resin film with a PET film was prepared by heating and drying at 140°C for 2 minutes.

[0050] (3. Preparation of Resin Plates) After stacking 20 sheets of the PET film-attached resin film obtained in "2. Preparation of Resin Films" above using vacuum lamination, a resin plate without glass cloth was prepared by press molding under the following conditions. -Press Molding Conditions- Heating conditions: The temperature was raised from 25°C to 230°C at a heating rate of 3°C / min, held at 230°C for 90 minutes, and then cooled for 30 minutes. Pressure conditions (pressure applied to the three prepregs sandwiched between copper foils): 3 MPa (from the start of heating to the end of cooling)

[0051] (4. Preparation of Prepreg) The PET film-attached resin film obtained in "2. Preparation of Resin Film" above was placed on both sides of a glass cloth "IPC#1010" (manufactured by Nitto Boseki Co., Ltd., thickness: 13 μm, S glass, size 250 mm x 250 mm) so that the resin layer surface of the PET film-attached resin film was in contact with the glass cloth. This laminate of "PET film / resin film / glass cloth / resin film / PET film" was heated and pressurized under vacuum using a vacuum laminating apparatus. In this way, a PET film-attached prepreg was obtained in which the thermosetting resin composition of the resin film was impregnated into the glass cloth. The vacuum lamination conditions were a heating plate temperature of 130°C, a pressing pressure of 1.0 MPa, a vacuum degree of 100 kPa or less, a vacuum time of 30 seconds, and a heating time of 30 seconds. The PET film was peeled off from the obtained PET film-attached prepreg to obtain a prepreg (thickness 110 μm). The thickness of the prepreg was measured at five locations: the four corners of the prepreg (10 mm from the edge of the prepreg) and the center. The average of the values ​​obtained by measuring these points using a horizontally adjusted base and a digital indicator (manufactured by Mitutoyo Corporation) was used. The thickness of the thermosetting resin composition layer overhanging the glass cloth was calculated by subtracting the thickness of the glass cloth from the thickness of the prepreg and multiplying the result by 1 / 2, which was found to be 50 μm.

[0052] (5. Fabrication of Copper-Clad Laminate) Three prepregs obtained in "4. Fabrication of Prepregs" were stacked, and 12 μm thick copper foil "GTS-12" (manufactured by Furukawa Electric Co., Ltd.) was placed above and below them. Next, a copper-clad laminate was fabricated by press molding under the following conditions. - Press molding conditions - Heating conditions: The temperature was raised from 25°C to 230°C at a heating rate of 3°C / min, held at 230°C for 90 minutes, and then cooled for 30 minutes. Pressure conditions (pressure applied to the three prepregs sandwiched between copper foils): 3 MPa (from the start of heating to the end of cooling)

[0053] (6. Evaluation of the Insulating Layer) The surface of the resin plate obtained by the above method (i.e., the surface of the insulating layer) was visually observed and evaluated according to the evaluation criteria below. In addition, the outer copper foil of the copper-clad laminate obtained by the above method was removed by immersion in a copper etching solution (10% by mass solution of ammonium persulfate, manufactured by Mitsubishi Gas Chemical Company, Inc.), and the surface of the exposed insulating layer was visually observed and evaluated according to the evaluation criteria below. The results for each are shown in Table 1. A: No molding defects (Resin plate: see Figure 2, Copper-clad laminate: see Figure 3) B: Some molding defects (Resin plate: see Figure 4, Copper-clad laminate: see Figure 5) C: Molding defects throughout (Resin plate: see Figure 6, Copper-clad laminate: see Figure 7)

[0054]

[0055] Details of each component listed in Table 1 are as follows: [(A) Component] Maleimide compound 1: Derivative of the maleimide compound obtained in Production Example 1 [(B) Inorganic filler] Inorganic filler 1: Spherical fused silica, volume average particle diameter = 10 μm Inorganic filler 2: Spherical fused silica, volume average particle diameter = 6.0 μm Inorganic filler 3: Spherical fused silica, volume average particle diameter = 3.0 μm (for comparison) Inorganic filler 4: Spherical fused silica, volume average particle diameter = 1.0 μm Inorganic filler 5: Spherical fused silica, volume average particle diameter = 0.5 μm The volume average particle diameter of the inorganic fillers was measured using the laser diffraction scattering particle size distribution analyzer "LA-920" (manufactured by Horiba, Ltd.).

[0056] [(C) Thermosetting resins] • Epoxy resin 1: "EP-4040", manufactured by ADEKA Corporation, viscosity at 25°C: 300 mPa·s, epoxy equivalent: 308 g / eq • Epoxy resin 2: "NC-7000-L", manufactured by Nippon Kayaku Co., Ltd., solid at 25°C, epoxy equivalent: 308 g / eq

[0057] [(D) Curing accelerators] ・Curing accelerator 1: "TBP2" (adduct of tri-n-butylphosphine and p-benzoquinone, manufactured by Kurogane Kasei Co., Ltd.) ・Curing accelerator 2: "2PZCNS-PW" (1-cyanoethyl-2-phenylimidazolium trimellitate, manufactured by Shikoku Kasei Holdings Co., Ltd.)

[0058] From the results in Table 1, it can be seen that in the case of the thermosetting resin compositions of Examples 1 to 5 containing components (A) to (B), molding defects were not or were suppressed in the insulating layer of the resin plate and copper-clad laminate, indicating high insulation reliability. Furthermore, since the content of component (B) in Examples 1 to 5 was 55% by volume or more, it can be said that the rigidity (elastic modulus) was high. On the other hand, in the case of the thermosetting resin compositions of Comparative Examples 1 to 2, which used an inorganic filler with a small particle size instead of component (B), when the content of the inorganic filler was increased to 55% by volume or more in order to increase rigidity (elastic modulus), a large number of molding defects occurred in the insulating layer of the resin plate and copper-clad laminate.

Claims

1. A thermosetting resin composition containing (A) a maleimide compound and (B) an inorganic filler with a volume average particle size of 2.5 μm or more.

2. The thermosetting resin composition according to claim 1, wherein the nitrogen atoms of the N-substituted maleimide group are bonded to each other via a linking group containing an aromatic ring.

3. The thermosetting resin composition according to claim 1, wherein the content of component (B) is 55% by volume or more relative to the total amount of solids.

4. The thermosetting resin composition according to claim 1, wherein component (B) is one or more selected from the group consisting of silica, alumina, titanium oxide, mica, beryllium, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, molybdate compounds, talc, aluminum borate, and silicon carbide.

5. The thermosetting resin composition according to claim 1, further comprising (C) a thermosetting resin (excluding component (A) above).

6. The thermosetting resin composition according to claim 1, for use as an interlayer insulating layer for printed circuit boards.

7. A prepreg containing the thermosetting resin composition described in claim 1 or a semi-cured product of the thermosetting resin composition.

8. A resin film containing the thermosetting resin composition described in claim 1 or a semi-cured product of the thermosetting resin composition.

9. A laminate comprising the resin film or cured product thereof described in claim 8, a support layer, and the resin film or cured product thereof described in claim 8, laminated in this order.

10. A laminate having a cured product of the thermosetting resin composition described in claim 1 and a metal foil.

11. A laminate having a cured prepreg according to claim 7, a cured resin film according to claim 8, or a cured laminate according to claim 9, and a metal foil.

12. A printed circuit board having a cured product of the thermosetting resin composition described in claim 1, a cured product of the prepreg described in claim 7, a cured product of the resin film described in claim 8, or a cured product of the laminate described in claim 9.

13. A semiconductor package having a printed circuit board according to claim 12 and a semiconductor element.

Images