Resin composition, prepreg, laminate, printed wiring board, semiconductor package, and method for producing printed wiring board

Abstract

To provide a resin composition excellent in drilling processability while maintaining good heat resistance and conductor adhesiveness, a prepreg, a laminate, a printed wiring board and a semiconductor package using the resin composition, and a method for producing a printed wiring board.SOLUTION: There are provided a resin composition containing (A) a thermosetting resin, (B) a molybdenum compound, and (C) one or more selected from the group consisting of fullerene and fullerene derivatives, a prepreg, a laminate, a printed wiring board, and a semiconductor package using the resin composition, and a method for manufacturing the printed wiring board.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present embodiment relates to a resin composition, a prepreg, a laminate, a printed wiring board, a semiconductor package, and a method for producing a printed wiring board. [Background technology]

[0002] In recent years, there has been an increasing demand for smaller size, lighter weight, higher wiring density, and faster processing speeds for printed wiring boards used in electronic devices, communication devices, etc. Accordingly, substrates for printed wiring boards are being required to have higher reliability than ever before.

[0003] Prepregs obtained by impregnating a fiber substrate such as glass cloth with a resin composition are used to manufacture substrates for printed wiring boards. For example, a laminate for printed wiring boards is manufactured by stacking multiple prepregs and heat-curing them. In some cases, substrates for printed wiring boards require drilling to connect the various layers, and the most common drilling method is a mechanical method using a drill. However, drill breakage can be a problem depending on the material of the substrate being drilled. Drill breakage can result in reduced quality and productivity of the substrate.

[0004] A technique of blending zinc molybdate into a resin composition is known as a method for improving the drillability of the resin composition. Patent Document 1 discloses a resin composition containing a molybdenum compound supported on inorganic particles. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-199562 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, substrates have been loaded with a high amount of inorganic filler to reduce the thermal expansion coefficient of the substrate, or harder fiber substrates have been used to increase the rigidity of the substrate, which requires better drillability than before. Furthermore, substrates for printed wiring boards are required to have good heat resistance, conductor adhesion, and other properties in addition to drillability. Therefore, it is desirable to improve drillability while maintaining good heat resistance and conductor adhesion.

[0007] In view of the current situation, an object of the present embodiment is to provide a resin composition that has excellent drill processability while maintaining good heat resistance and conductor adhesion, a prepreg, a laminate, a printed wiring board, and a semiconductor package that use the resin composition, and a method for producing a printed wiring board. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the present embodiment described below, and have completed the present embodiment. [1] (A) a thermosetting resin; (B) a molybdenum compound; (C) one or more members selected from the group consisting of fullerenes and fullerene derivatives; A resin composition comprising: [2] The component (C) is fullerene C 60 and fullerene C 70 The resin composition according to the above [1], which contains one or more selected from the group consisting of: [3] The resin composition according to the above [1] or [2], wherein the content of the (B) molybdenum compound is 0.01 to 5.0 mass % relative to the total amount (100 mass %) of solids in the resin composition. [4] The resin composition according to any one of the above [1] to [3], wherein the content of the component (C) is 0.1 to 20 mass % relative to the total solid content (100 mass %) of the resin composition. [5] The resin composition according to any one of the above [1] to [4], wherein the ratio of the volumetric content of the component (C) to the volumetric content of the component (B) [(C) / (B)] is 0.01 to 2.0. [6] The resin composition according to any one of the above [1] to [5], further comprising (D) an inorganic filler. [7] The resin composition according to any one of the above [1] to [6], wherein the content of the (D) inorganic filler is 20 to 95 mass % relative to the total solid content (100 mass %) of the resin composition. [8] A prepreg comprising the resin composition according to any one of the above [1] to [7] and a fiber base material. [9] The prepreg according to [8] above, wherein the fiber base material is glass cloth.

[10] A laminate comprising a cured product of the resin composition according to any one of the above [1] to [7] and a metal foil.

[11] A printed wiring board having a cured product of the resin composition according to any one of [1] to [7] above.

[12] A semiconductor package comprising the printed wiring board according to

[11] above and a semiconductor element.

[13] A method for producing a printed wiring board, comprising using a drill to drill holes in at least one selected from the group consisting of a cured product of the resin composition described in any one of [1] to [7] above, a cured product of a prepreg containing the resin composition described in any one of [1] to [7] above and a fiber base material, and a laminate having a cured product of the resin composition described in any one of [1] to [7] above and a metal foil. [Effects of the Invention]

[0009] According to the present embodiment, it is possible to provide a resin composition that has excellent drill processability while maintaining good heat resistance and conductor adhesion, a prepreg, a laminate, a printed wiring board, a semiconductor package, and a method for producing a printed wiring board, which use the resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0010] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. For example, the expression "X to Y" (X and Y are real numbers) means a range of values ​​equal to or greater than X and equal to or less than Y. In this specification, the expression "equal to or greater than X" means X and a value greater than X. In this specification, the expression "equal to or less than Y" means Y and a value less than Y. The lower and upper limits of any numerical range described herein may be combined with any lower or upper limit of any other numerical range. In the numerical ranges described in this specification, the lower or upper limit of the numerical range may be replaced with values ​​shown in the examples.

[0011] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more. In this specification, the content of each component in a resin composition means the total amount of the multiple substances present in the resin composition, unless otherwise specified, when multiple substances corresponding to each component are present in the resin composition.

[0012] In this specification, the term "solid content" refers to components other than the solvent, and components that are liquid at 25°C are also considered to be solid content.

[0013] The expression "containing XX" as used herein means both containing XX in a reacted state if XX is capable of reacting, and simply containing XX.

[0014] The weight average molecular weight (Mw) in this specification refers to a value measured in terms of polystyrene by gel permeation chromatography (GPC). Specifically, the weight average molecular weight (Mw) in this specification can be measured by the method described in the examples.

[0015] In this specification, the term "semi-cured product" is synonymous with a resin composition in a B-stage state according to JIS K 6800 (2006), and the term "cured product" is synonymous with a resin composition in a C-stage state according to JIS K 6800 (2006).

[0016] The mechanism of action described in this specification is speculation and does not limit the mechanism by which the effects of this embodiment are achieved.

[0017] Any combination of the features described in this specification is also included in this embodiment.

[0018] [Resin composition] The resin composition of the present embodiment is (A) a thermosetting resin; (B) a molybdenum compound; (C) one or more members selected from the group consisting of fullerenes and fullerene derivatives; The resin composition contains:

[0019] The components constituting the resin composition of the present embodiment will be described below in order. In this specification, the term "resin component" refers to a resin and a compound that forms a resin through a curing reaction. In the resin composition of this embodiment, for example, the thermosetting resin (A) corresponds to the resin component. When the resin composition of this embodiment contains, as optional components, resins or compounds that form resins by a curing reaction in addition to the above components, these optional components are also included in the resin component. The components (B) and (C) are not included in the resin component.

[0020] <(A) Thermosetting resin> The (A) thermosetting resin is not particularly limited. (A) Examples of thermosetting resins include epoxy resins, phenolic resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. The (A) thermosetting resin may be used alone or in combination of two or more. Among these, as the (A) thermosetting resin, maleimide resin, epoxy resin, and cyanate resin are preferred from the viewpoints of heat resistance and conductor adhesion, and maleimide resin is more preferred.

[0021] (maleimide resin) When the resin composition of the present embodiment contains a maleimide resin, the heat resistance and conductor adhesion of the insulating layer tend to be more favorable. The maleimide resin may be used alone or in combination of two or more.

[0022] The maleimide resin is preferably at least one selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of such maleimide resins. In the following description, a maleimide resin having one or more N-substituted maleimide groups may be referred to as a "maleimide resin (AX)" or an "(AX) component." Furthermore, a derivative of a maleimide resin having one or more N-substituted maleimide groups may be referred to as a "maleimide resin derivative (AY)" or an "(AY) component."

[0023] (Maleimide resin (AX)) From the viewpoint of the conductor adhesion and heat resistance of the insulating layer, the maleimide resin (AX) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups, and more preferably an aromatic bismaleimide resin having two N-substituted maleimide groups. In this specification, "aromatic maleimide resin" refers to a compound having an N-substituted maleimide group directly bonded to an aromatic ring. In addition, in this specification, "aromatic bismaleimide resin" refers to a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. In addition, in this specification, "aromatic polymaleimide resin" refers to a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring. In addition, in this specification, "aliphatic maleimide resin" refers to a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0024] The maleimide resin (AX) is preferably a maleimide resin represented by the following general formula (A-1).

[0025] [ka] (In the formula, X A1 is a divalent organic group.

[0026] X in the above general formula (A-1) A1 Examples of the divalent organic group represented by the formula include divalent organic groups represented by the following general formula (A-2), (A-3), (A-4), (A-5), or (A-6):

[0027] [ka] (In the formula, R A1 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A1 is an integer from 0 to 4. * represents a binding site.

[0028] R in the above general formula (A-2) A1Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. n in the above general formula (A-2) A1 is preferably an integer of 0 to 2, and more preferably 0.

[0029] [ka] (In the formula, R A2 and R A3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent organic group represented by the following general formula (A-3-1): A2 and n A3 are each independently an integer of 0 to 4. * represents a binding site.

[0030] R in the above general formula (A-3) A2 and R A3 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by the above R A1 The same can be mentioned. X in the above general formula (A-3) A2 Examples of the alkylene group having 1 to 5 carbon atoms represented by include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. Among these, an alkylene group having 1 to 3 carbon atoms is preferred, and a methylene group is more preferred. X in the above general formula (A-3) A2Examples of the alkylidene group having 2 to 5 carbon atoms represented by include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. n in the above general formula (A-3) A2 and n A3 is preferably an integer of 0 to 3, more preferably 0 or 2. A2 or n A3 is an integer equal to or greater than 2, multiple R A2 R A3 They may be the same or different from each other.

[0031] X in the above general formula (A-3) A2 The divalent organic group represented by the general formula (A-3-1) is as follows:

[0032] [ka] (In the formula, R A4 and R A5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A3 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. A4 and n A5 are each independently an integer of 0 to 4. * represents a binding site.

[0033] R in the above general formula (A-3-1) A4 and R A5 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by the above R A1 The same can be mentioned. X in the above general formula (A-3-1) A3 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the above X A2 The same can be mentioned. n in the above general formula (A-3-1) A4 and nA5 is preferably an integer of 0 to 2, more preferably 0. A4 or n A5 is an integer equal to or greater than 2, multiple R A4 R A5 They may be the same or different from each other.

[0034] [ka] (In the formula, n A6 is an integer between 0 and 10. * represents a binding site.

[0035] [ka] (In the formula, n A7 is a number between 0 and 5. * represents a binding site.

[0036] [ka] (In the formula, R A6 and R A7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. A8 is an integer from 1 to 8. * represents a binding site.

[0037] R in the above general formula (A-6) A6 and R A7 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by the above R A1 The same as n A8 is an integer equal to or greater than 2, multiple R A6 R A7 They may be the same or different from each other.

[0038] Examples of the maleimide resin (AX) include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins, and among these, aromatic bismaleimide resins are preferred. Examples of the maleimide resin (AX) include bis(4-maleimidophenyl)methane, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 4-methyl-1,3-phenylene bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, aromatic bismaleimide resins having an indane skeleton, biphenylaralkyl maleimide resins, etc. Among these, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane is preferred.

[0039] (Maleimide resin derivative (AY)) The maleimide resin derivative (AY) is preferably a resin containing a structure derived from a maleimide resin having one or more N-substituted maleimide groups (i.e., the maleimide resin (AX)) and a structure derived from a diamine compound [hereinafter, sometimes referred to as "aminomaleimide resin"].

[0040] An example of a structure derived from the maleimide resin (AX) contained in the aminomaleimide resin is a structure formed by a Michael addition reaction between at least one N-substituted maleimide group among the N-substituted maleimide groups contained in the maleimide resin (AX) and an amino group contained in the diamine compound. The content of the structure derived from the maleimide resin (AX) in the aminomaleimide resin is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and even more preferably 60 to 90% by mass. The structure derived from the maleimide resin (AX) contained in the aminomaleimide resin may be of one type alone or may be of two or more types.

[0041] An example of a structure derived from a diamine compound contained in an aminomaleimide resin is a structure formed by a Michael addition reaction between one or both of two amino groups contained in a diamine compound and an N-substituted maleimide group contained in the maleimide resin (AX). The content of the structure derived from the diamine compound in the aminomaleimide resin is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and even more preferably 10 to 40% by mass. The structure derived from the diamine compound contained in the aminomaleimide resin may be of one type alone or of two or more types.

[0042] The amino group contained in the diamine compound is preferably a primary amino group. As the diamine compound, an aromatic diamine compound having two amino groups directly bonded to an aromatic ring, or a silicone compound having two primary amino groups is preferred.

[0043] Examples of the aromatic diamine compound include 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, and 3,3'-diethyl-4,4'-diaminodiphenylmethane.

[0044] As the silicone compound having two primary amino groups, a silicone compound having primary amino groups at both ends is preferred, and polydimethylsiloxane having primary amino groups at both ends is more preferred. The primary amino group equivalent weight of the silicone compound having two primary amino groups is preferably 300 to 2,000 g / mol, more preferably 400 to 1,500 g / mol, and even more preferably 500 to 1,000 g / mol.

[0045] In the resin composition of the present embodiment, the content of the (A) thermosetting resin is preferably 20 to 99% by mass, more preferably 30 to 98% by mass, still more preferably 50 to 96% by mass, and even more preferably 70 to 94% by mass with respect to the total amount (100% by mass) of the resin components in the resin composition. When the content of the (A) thermosetting resin is not less than the above lower limit value, the heat resistance, moldability, workability, and conductor adhesion tend to be better. Also, when the content of the (A) thermosetting resin is not more than the above upper limit value, the dielectric properties tend to be better.

[0046] <(B) Molybdenum compound> (B) The molybdenum compound is not particularly limited as long as it is a compound containing molybdenum. (B) The molybdenum compound may be used alone or in combination of two or more.

[0047] (B) Examples of the molybdenum compound include metal molybdate, molybdenum oxide, ammonium molybdate, etc. Among these, from the viewpoints of drillability and conductor adhesion, metal molybdate is preferred. Examples of the metal molybdate include zinc molybdate, magnesium molybdate, calcium molybdate, strontium molybdate, barium molybdate, lithium molybdate, sodium molybdate, potassium molybdate, copper molybdate, iron molybdate, zirconium molybdate, etc. Among these, from the viewpoints of drillability and conductor adhesion, zinc molybdate is preferred. Note that the zinc molybdate in the present embodiment is a salt of molybdic acid and zinc, and its compositional formula is Zn X Mo Y O4 (0.5 < X < 2.5, 0.5 < Y < 2.5), Zn X Mo Y O4(OH) Z (0.5 < X < 2.5, 0.5 < Y < 2.5, 0.5 < Z < 2.5), etc.

[0048] (B) The molybdenum compound may be supported on a carrier. Hereinafter, a compound composed of a carrier and a molybdenum compound supported on the carrier will be referred to as a "supported molybdenum compound." As the carrier for the supported molybdenum compound, for example, inorganic particles can be used. Examples of inorganic particles include inorganic oxide particles such as talc, silica, and alumina, and among these, talc is preferred. The loading rate of the molybdenum compound in the supported molybdenum compound is preferably 5 to 40 mass%, more preferably 10 to 35 mass%, and even more preferably 15 to 30 mass%. The loading rate of the molybdenum compound means the ratio of the mass of the molybdenum compound to the total mass of the supported molybdenum compound.

[0049] Average particle size of the supported molybdenum compound (D 50 ) is preferably 0.5 to 10.0 μm, more preferably 1.0 to 7.0 μm, and even more preferably 2.0 to 4.0 μm. In this specification, the average particle diameter (D 50 ) is the particle size at the point corresponding to 50% volume when the cumulative frequency distribution curve of particle size is calculated assuming the total volume of particles is 100%. 50 ) can be measured, for example, by a particle size distribution measuring device using a laser diffraction scattering method. The particle shape of the supported molybdenum compound is not particularly limited, and examples thereof include spherical and crushed shapes.

[0050] In the resin composition of this embodiment, the content of the (B) molybdenum compound is, from the viewpoint of further improving drill processability, preferably 0.01 mass % or more, more preferably 0.1 mass % or more, even more preferably 0.3 mass % or more, and still more preferably 0.5 mass % or more, relative to the total solid content (100 mass %) of the resin composition. Furthermore, from the viewpoint of easily obtaining better conductor adhesion, the content of the (B) molybdenum compound is preferably 5.0 mass% or less, more preferably 3.0 mass% or less, even more preferably 2.0 mass% or less, and even more preferably 1.0 mass% or less, relative to the total solid content (100 mass%) of the resin composition. From the same viewpoint as above, the content of the (B) molybdenum compound is preferably 0.01 to 5.0 mass%, more preferably 0.1 to 3.0 mass%, even more preferably 0.3 to 2.0 mass%, and still more preferably 0.5 to 1.0 mass%, relative to the total solid content (100 mass%) of the resin composition. When the molybdenum compound (B) is a supported molybdenum compound, the content of the molybdenum compound (B) does not include the content of the carrier, but means the content of the supported molybdenum compound.

[0051] When the resin composition of the present embodiment contains a supported molybdenum compound as the (B) molybdenum compound, the content of the supported molybdenum compound is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 1.0 mass % or more, and still more preferably 3.0 mass % or more, relative to the total solid content (100 mass %) of the resin composition, from the viewpoint of further improving drilling processability. Furthermore, from the viewpoint of easily obtaining better conductor adhesion, the content of the supported molybdenum compound is preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 10 mass% or less, and even more preferably 5.0 mass% or less, relative to the total solid content (100 mass%) of the resin composition. From the same viewpoint as above, the content of the supported molybdenum compound is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, even more preferably 1.0 to 10 mass%, and still more preferably 3.0 to 5.0 mass%, relative to the total solid content (100 mass%) of the resin composition.

[0052] <(C) One or more members selected from the group consisting of fullerenes and fullerene derivatives> The resin composition of the present embodiment further contains (C) one or more types selected from the group consisting of fullerenes and fullerene derivatives (hereinafter also referred to as "(C) fullerenes"). Here, the term "fullerene" in this embodiment refers to a closed-shell polyhedron composed of n tricoordinate carbon atoms, having 12 five-membered rings and (n / 2-10) six-membered rings, where n is an integer of 20 or more. The resin composition of this embodiment contains (C) fullerenes in addition to the (B) molybdenum compound, thereby improving drillability while maintaining good heat resistance and conductor adhesion. The reason for this is unclear, but it is thought that the (C) fullerenes, together with the (B) molybdenum compound, play a role in protecting the drill surface, thereby improving drillability, and that the (C) fullerenes themselves have low volatility and are unlikely to interfere with the resin's inherent adhesion to the conductor, thereby maintaining good heat resistance and conductor adhesion. The component (C) may be used alone or in combination of two or more.

[0053] Examples of the component (C) include fullerene C 60 , fullerene C 70 , fullerene C 76 , fullerene C 78 , fullerene C 80 , fullerene C 82 , fullerene C 84 , fullerene C 90 , fullerene C 96 , fullerene C 240 , fullerene C 540 fullerenes such as tetrafluoroethylene, ... Examples of fullerene derivatives include fullerenes to which a substituent has been added, such as a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an amino group, an ester group, a carboxyl group, a carbonyl group, an oxycarbonyl group, an acetyl group, a sulfonyl group, a silyl group, a nitrile group, an alkyl group, a perfluoroalkyl group, an alkenyl group, an alkynyl group, an alkenyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an aromatic ring group. Among these, fullerene C is preferred from the viewpoint of further improving drilling processability while maintaining good heat resistance and conductor adhesion. 60 and fullerene C 70 It is preferable that the composition contains one or more selected from the group consisting of:

[0054] In the resin composition of this embodiment, the content of component (C) is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, even more preferably 1.0 mass % or more, and even more preferably 1.5 mass % or more, relative to the total solid content (100 mass %) of the resin composition, from the viewpoint of further improving drill processability while maintaining good heat resistance and conductor adhesion. Furthermore, from the viewpoint of easily obtaining better dispersibility of the (C) component, the content of the (C) component is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and even more preferably 5.0% by mass or less, relative to the total solid content (100% by mass) of the resin composition. From the same viewpoint as above, the content of component (C) is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, even more preferably 1.0 to 10 mass%, and even more preferably 1.5 to 5.0 mass%, relative to the total solid content (100 mass%) of the resin composition.

[0055] The ratio of the volumetric content of the (C) component to the volumetric content of the (B) component [(C) / (B)] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.10 or more, and even more preferably 0.20 or more, from the viewpoint of further improving drilling processability while maintaining good heat resistance and conductor adhesion. Furthermore, the content ratio [(C) / (B)] is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.0 or less, and even more preferably 0.40 or less, from the viewpoint of further improving drilling processability while maintaining good heat resistance and conductor adhesion. From the same viewpoint as above, the ratio of the volumetric content of the (C) component to the volumetric content of the (B) component [(C) / (B)] is preferably 0.01 to 2.0, more preferably 0.05 to 1.5, even more preferably 0.10 to 1.0, and still more preferably 0.20 to 0.40.

[0056] <(D) Inorganic filler> The resin composition of the present embodiment preferably further contains (D) an inorganic filler. The resin composition of the present embodiment tends to have better low thermal expansion properties and heat resistance due to the inclusion of (D) inorganic filler. The (D) inorganic filler may be used alone or in combination of two or more kinds.

[0057] Examples of (D) inorganic fillers include silica, alumina, titanium oxide, mica, beryllia, 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, talc, aluminum borate, silicon carbide, etc. Among these, from the viewpoints of low thermal expansion, heat resistance, and flame retardancy, silica, alumina, mica, and talc are preferred, silica and alumina are more preferred, and silica is even more preferred.

[0058] When the resin composition of this embodiment contains (D) an inorganic filler, the content of (D) the inorganic filler is preferably 20 to 95 mass %, more preferably 30 to 80 mass %, and even more preferably 40 to 60 mass %, relative to the total solid content (100 mass %) of the resin composition. When the content of the (D) inorganic filler is equal to or greater than the lower limit, the low thermal expansion and heat resistance tend to be improved. When the content of the (D) inorganic filler is equal to or less than the upper limit, the moldability and conductor adhesion tend to be improved.

[0059] In the present embodiment, the ratio of the total content of the (B) molybdenum compound and the (C) fullerenes to the total content of the (B) molybdenum compound, the (C) fullerenes, and the (D) inorganic filler [((B)+(C)) / ((B)+(C)+(D))] is preferably 0.01 to 0.5, more preferably 0.05 to 0.3, and even more preferably 0.08 to 0.2, on a mass basis, from the viewpoint of further improving drilling processability while maintaining good heat resistance and conductor adhesion.

[0060] <(E) Curing accelerator> The resin composition of the present embodiment preferably further contains (E) a curing accelerator. The resin composition of the present embodiment contains the curing accelerator (E), which improves the curability and tends to easily provide better conductor adhesion. The (E) curing accelerator may be used alone or in combination of two or more.

[0061] Examples of the (E) curing accelerator include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, tributylamine, pyridine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate; isocyanate-masked imidazole compounds such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; quaternary ammonium compounds; and phosphorus compounds such as triphenylphosphine and quaternary phosphonium compounds which are addition reaction products of p-benzoquinone and tri-n-butylphosphine. peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy)diisopropylbenzene; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile); carboxylates of manganese, cobalt, zinc, and the like; and acidic catalysts such as p-toluenesulfonic acid.

[0062] When the resin composition of the present embodiment contains the (E) curing accelerator, the content of the (E) curing accelerator is preferably 0.05 to 1.0 part by mass, more preferably 0.10 to 0.60 parts by mass, and even more preferably 0.15 to 0.30 parts by mass, relative to 100 parts by mass of the (A) thermosetting resin. When the content of the (E) curing accelerator is equal to or greater than the lower limit, a sufficient curing acceleration effect tends to be easily obtained, and when the content of the (E) curing accelerator is equal to or less than the upper limit, the storage stability tends to be more easily improved.

[0063] <(F) Other Ingredients> The resin composition of the present embodiment may further contain other components, as necessary, such as a thermoplastic resin, a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, a silane coupling agent, an organic solvent, and other additives. The other components may each be used alone or in combination of two or more. The content of the above-described optional components in the resin composition of this embodiment is not particularly limited, and they may be used as needed within a range that does not impair the effects of this embodiment. Furthermore, the resin composition of the present embodiment may not contain the above-mentioned optional components depending on the desired performance.

[0064] (thermoplastic resin) Examples of thermoplastic resins include styrene-based thermoplastic resins, olefin-based thermoplastic resins, urethane-based thermoplastic resins, polyester-based thermoplastic resins, polyamide-based thermoplastic resins, acrylic-based thermoplastic resins, and silicone-based thermoplastic resins. When the resin composition of the present embodiment contains a thermoplastic resin, the content of the thermoplastic resin is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of the total resin components in the resin composition.

[0065] (organic solvent) The resin composition of the present embodiment may contain an organic solvent from the viewpoint of ease of handling. In this specification, a resin composition containing an organic solvent may be referred to as a resin varnish. Examples of organic solvents 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 hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone.

[0066] In the resin composition of the present embodiment, the content of aluminum hydroxide is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 1% by mass or less, relative to the total solid content (100% by mass) of the resin composition, from the viewpoint of heat resistance, and may be 0% by mass. In the resin composition of this embodiment, the content of boron nitride is preferably 20 mass % or less, more preferably 10 mass % or less, and even more preferably 1 mass % or less, relative to the total solid content (100 mass %) of the resin composition, from the viewpoint of conductor adhesion, and may be 0 mass %.

[0067] The total content of the resin components in the resin composition of this embodiment is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, and even more preferably 30 to 50 mass%, relative to the total solid content (100 mass%) of the resin composition, from the viewpoints of low thermal expansion, heat resistance, flame retardancy, and conductor adhesion.

[0068] <Method of manufacturing resin composition> The resin composition of the present embodiment can be produced by mixing the components. At this time, the components may be dissolved or dispersed while being stirred. The mixing conditions, such as the order of mixing, temperature, and time, are not particularly limited and may be set as desired depending on the types of raw materials, etc.

[0069] [Prepreg] The prepreg of the present embodiment is a prepreg containing the resin composition of the present embodiment or a semi-cured product of the resin composition. The prepreg of the present embodiment contains the resin composition of the present embodiment or a semi-cured product of the resin composition, and a sheet-like fiber substrate.

[0070] As the sheet-like fiber base material contained in the prepreg of this embodiment, known sheet-like fiber base materials used in various laminates for electrical insulating materials can be used. Examples of materials for the sheet-like fiber substrate include inorganic fibers such as E-glass, D-glass, S-glass, and Q-glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like fiber substrates come in the form of woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, and the like.

[0071] The prepreg of this embodiment can be produced, for example, by impregnating or applying the resin composition of this embodiment to a sheet-like fiber substrate, and then heating and drying it to bring it to a B-stage. The temperature and time for heat drying can be, for example, 50 to 200° C. and 1 to 30 minutes, from the viewpoints of productivity and appropriately bringing the resin composition of this embodiment into a B-stage.

[0072] The content of the resin composition in the prepreg of this embodiment is preferably 20 to 90 mass%, more preferably 25 to 80 mass%, and even more preferably 30 to 75 mass%, from the viewpoint of easily obtaining better moldability when made into a laminate.

[0073] The thickness of the prepreg may be adjusted appropriately depending on the application, but from the viewpoint of moldability and workability, it is preferably 20 to 500 μm, more preferably 40 to 400 μm, even more preferably 60 to 300 μm, and even more preferably 80 to 200 μm.

[0074] [Laminate] The laminate of this embodiment is a laminate having a cured product of the resin composition of this embodiment and a metal foil. A laminate having a metal foil is sometimes called a metal-clad laminate.

[0075] The laminate of this embodiment can be produced, for example, by arranging metal foil on one or both sides of the prepreg of this embodiment and then molding it under heat and pressure. Usually, the B-staged prepreg is cured by this heat and pressure molding to obtain the laminate of this embodiment. When hot-press molding is performed, only one prepreg may be used, or two or more prepregs may be laminated together. For the hot pressure molding, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used. The conditions for the hot pressing can be, for example, a temperature of 100 to 300° C., a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.

[0076] Examples of metals for the metal foil include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements.

[0077] The thickness of the laminate of this embodiment may be adjusted appropriately depending on the application, but from the viewpoint of suppressing warpage, it is preferably 200 μm or more, more preferably 400 μm or more, even more preferably 600 μm or more, and even more preferably 800 μm or more. Furthermore, the thickness of the laminate may be 3,000 μm or less, 2,000 μm or less, or 1,500 μm or less, as desired.

[0078] [Printed wiring board and print manufacturing method] The printed wiring board of this embodiment is a printed wiring board having a cured product of the resin composition of this embodiment. Examples of methods for producing printed wiring boards of this embodiment include methods of forming conductor circuits on one or more selected from the group consisting of a cured product of the resin composition of this embodiment, a cured product of a prepreg containing the resin composition of this embodiment and a fiber base material, and a laminate having a cured product of the resin composition of this embodiment and a metal foil. The conductor circuits can be formed by known methods, for example, by appropriately applying metal plating, etching of metal foil, etc. The method for producing a printed wiring board of this embodiment is preferably a method for drilling holes using a drill in one or more materials selected from the group consisting of a cured product of the resin composition of this embodiment, a cured product of a prepreg containing the resin composition of this embodiment and a fiber base material, and a laminate having a cured product of the resin composition of this embodiment and a metal foil. Conventionally known methods can be used for drilling holes. Furthermore, if necessary, a multilayer adhesive process may be carried out to produce a multilayer printed wiring board.

[0079] [Semiconductor Package] The semiconductor package of this embodiment is a semiconductor package that includes the printed wiring board of this embodiment and a semiconductor element. The semiconductor package of this embodiment can be manufactured by, for example, mounting a semiconductor chip, a memory, and the like on the printed wiring board of this embodiment by a known method. [Example]

[0080] The present embodiment will be specifically described below with reference to examples, although the present embodiment is not limited to the following examples.

[0081] In each example, the weight average molecular weight (Mw) was measured by the following procedure. (Method for measuring weight average molecular weight (Mw)) The weight-average molecular weight (Mw) was calculated by gel permeation chromatography (GPC) using a calibration curve prepared using standard polystyrene. The calibration curve was approximated by a cubic equation using standard polystyrene: TSKstandard POLYSTYRENE (Types: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name]. The GPC measurement conditions are shown below. [GPC measurement conditions] Equipment: High-speed GPC equipment HLC-8320GPC Detector: UV-8320 ultraviolet absorption detector [manufactured by Tosoh Corporation] Column: Guard column: TSK Guardcolumn SuperHZ-L + Column: TSKgel SuperHZM-N + TSKgel SuperHZM-M + TSKgel SuperH-RC (all manufactured by Tosoh Corporation, product names) Column dimensions: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column) Eluent: tetrahydrofuran Sample concentration: 10mg / 5mL Injection volume: 25μL Flow rate: 1.00mL / min Measurement temperature: 40℃

[0082] Manufacturing Example 1 (Production of aminomaleimide resin) A 5-liter reactor equipped with a thermometer, a stirrer, and a reflux condenser and moisture content monitor was charged with 100 parts by weight of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 5.6 parts by weight of a silicone compound (primary amino group equivalent: 750 g / mol) containing primary amino groups at both ends, 7.9 parts by weight of 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 171 parts by weight of propylene glycol monomethyl ether. The mixture was refluxed for 2 hours and then concentrated at reflux for 3 hours to produce an aminomaleimide resin solution with a solids concentration of 65% by weight. The weight-average molecular weight (Mw) of the resulting aminomaleimide resin was approximately 2,700.

[0083] Example 1, Comparative Examples 1 to 6 (Production of Resin Composition) A varnish-like resin composition with a solid content of 60% by mass was prepared by stirring and mixing each of the components listed in Table 1 with methyl ethyl ketone. In Table 1, the unit of the blending amount of each component is parts by mass, and in the case of a solution, it means parts by mass converted into solid content. The volume contents of the components (B), (C), and (C') were calculated from the mass-based blend amounts and densities of the respective components.

[0084] (Prepreg manufacturing) The varnish-like resin composition obtained above was applied to a glass cloth (basis weight: 114 g / m 2 The resin composition was impregnated into a glass cloth (glass type: T glass, glass cloth thickness: 98 μm) and dried by heating at 120° C. for 3 minutes to obtain a prepreg (thickness: 99 μm). The content of the resin composition in the prepreg was 50% by mass.

[0085] (Manufacturing copper clad laminates) Twelve sheets of the prepreg obtained above were stacked, and 12 μm thick copper foil (manufactured by Mitsui Kinzoku Co., Ltd., product name "3EC-M3-VLP-12", roughened surface Rz: 3.0 μm) was placed on top and bottom of them so that the roughened surface was in contact with the prepreg. This laminate was heated and press-molded at a temperature of 240°C and a pressure of 3.0 MPa for 90 minutes to obtain a copper-clad laminate (thickness: 1212 μm).

[0086] [Evaluation method] The evaluations were carried out according to the following methods, and the results are shown in Table 1.

[0087] (Method for measuring glass transition temperature) The copper foil on both sides of the copper-clad laminate prepared in each example was removed by etching, and the laminate was cut into 2 mm x 40 mm pieces to prepare test specimens. Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMA Q800"), the test specimens were subjected to dynamic viscoelasticity analysis under the conditions of a measurement temperature range of 40 to 350°C, a heating rate of 5°C / min, and a frequency of 10 Hz to obtain the glass transition temperature. The glass transition temperature was determined as the temperature at which tanδ reached its maximum value in the temperature-loss tangent (tanδ) curve obtained.

[0088] (Method for measuring copper foil peel strength) The copper foil of the copper-clad laminate prepared above was etched into a 5 mm wide straight line to prepare a test piece. The resulting straight line copper foil was attached to a small tabletop tester (Shimadzu Corporation, product name "EZ-TEST") and peeled at 25°C in a 90° direction to measure the copper foil peel strength. The pulling speed during the copper foil peeling was 50 mm / min.

[0089] (Evaluation of drilling workability) Two copper-clad laminates were stacked, with a 0.15 mm thick aluminum foil placed on top and a 1.5 mm thick paper phenolic sheet placed underneath. Next, holes were drilled using a drilling machine (manufactured by Via Mechanics Co., Ltd., product name "ND-1V212") equipped with a φ0.15 mm drill manufactured by Union Tool Co., Ltd., at a rotation speed of 250 krpm and a feed rate of 2.5 m / min under the same conditions for each example. A maximum of 10,000 holes were drilled per drill, and the number of five drills that broke before drilling 10,000 holes was counted.

[0090] [Table 1]

[0091] The details of each component shown in Table 1 are as follows:

[0092] [Component (A)] Thermosetting resin: aminomaleimide resin produced in Production Example 1

[0093] [(B) Component] Zinc molybdate-supported talc: Zinc molybdate loading rate is 20 mass%, average particle diameter (D 50 )3.0μm, density 2.8g / cm 3

[0094] [(C) component] Fullerene: Carbon Frontier Co., Ltd., product name "nanom mix ST", C 60 and C 70 Mixed fullerenes (C 60 The content of is 50 to 65 mass%, C 70 content of 15-25% by mass, density 5.6 g / cm 3

[0095] [(C') component] Zinc molybdate (unsupported): Average particle size (D 50 ) 0.9 μm Boron nitride 1: Average particle size (D 50 ) 0.7 μm Boron nitride 2: average particle diameter (D 50 ) 10 μm Aluminum hydroxide: average particle size (D 50 ) 1.2 μm

[0096] [(D) component] Inorganic filler: spherical silica

[0097] It can be seen from Table 1 that the resin composition of Example 1 of this embodiment has excellent drilling processability while maintaining good heat resistance and copper foil peel strength.

Claims

1. (A) a thermosetting resin; (B) a molybdenum compound; (C) one or more selected from the group consisting of fullerenes and fullerene derivatives; A resin composition comprising:

2. The component (C) is fullerene C ６０ and fullerene C ７０ The resin composition according to claim 1, comprising one or more selected from the group consisting of:

3. 3. The resin composition according to claim 1, wherein the content of the molybdenum compound (B) is 0.01 to 5.0 mass% relative to the total solid content (100 mass%) of the resin composition.

4. The resin composition according to claim 1 or 2, wherein the content of the component (C) is 0.1 to 20 mass% relative to the total solid content (100 mass%) of the resin composition.

5. The resin composition according to claim 1 or 2, wherein the ratio [(C) / (B)] of the volume-based content of the (C) component to the volume-based content of the (B) component is 0.01 to 2.

0.

6. The resin composition according to claim 1 or 2, further comprising (D) an inorganic filler.

7. The resin composition according to claim 1 or 2, wherein the content of the (D) inorganic filler is 20 to 95 mass% relative to the total solid content (100 mass%) of the resin composition.

8. A prepreg comprising the resin composition according to claim 1 or 2 and a fiber base material.

9. The prepreg according to claim 8, wherein the fiber base material is glass cloth.

10. A laminate comprising a cured product of the resin composition according to claim 1 or 2 and a metal foil.

11. A printed wiring board comprising a cured product of the resin composition according to claim 1 or 2.

12. A semiconductor package comprising the printed wiring board according to claim 11 and a semiconductor element.

13. A method for producing a printed wiring board, comprising using a drill to drill holes in at least one selected from the group consisting of a cured product of the resin composition according to claim 1 or 2, a cured product of a prepreg containing the resin composition according to claim 1 or 2 and a fiber base material, and a laminate having a cured product of the resin composition according to claim 1 or 2 and a metal foil.

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