Prepregs, laminates, printed circuit boards, and semiconductor packages

Abstract

The present invention provides a prepreg with excellent drillability and copper foil adhesion, a laminate using the prepreg, a printed circuit board, and a semiconductor package. [Solution] The present invention provides a resin composition containing (A) a thermosetting resin and (B) spherical zinc molybdate, and a fiber base material, wherein the basis weight of the fiber base material is 50 g / m². 2 The above describes prepregs, laminates using the prepregs, printed circuit boards, and semiconductor packages.

Description

[Technical Field]

[0001] This embodiment relates to prepregs, laminates, printed circuit boards, and semiconductor packages. [Background technology]

[0002] In recent years, there has been a growing demand for miniaturization, weight reduction, higher wiring density, and faster processing speeds for printed circuit boards used in electronic devices, communication equipment, and other applications. Consequently, the insulating layers of printed circuit boards are increasingly required to have higher reliability than before.

[0003] Prepregs, obtained by impregnating a fibrous substrate such as glass cloth with a resin composition, are used as insulating materials for printed circuit boards. In the manufacturing process of printed circuit boards, drilling holes is sometimes performed on the cured prepreg. However, especially when the basis weight of the fibrous substrate is high, the hardness of the fibrous substrate can lead to a decrease in drill hole position accuracy and other deteriorations in drillability. Furthermore, in recent years, in order to lower the thermal expansion coefficient of the insulating layer, inorganic fillers are sometimes used at high concentrations, or harder fibrous substrates are sometimes employed. In such cases, the deterioration of drillability becomes even more pronounced.

[0004] A known technique involves incorporating zinc molybdate into a resin composition to improve its drillability. 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 Publication No. 2019-199562 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, studies by the present inventors have revealed that prepregs formed using a resin composition containing a molybdenum compound supported on inorganic particles have poor adhesion to copper foil (hereinafter also referred to as "copper foil adhesion").

[0007] In view of the current situation, this embodiment aims to provide a prepreg with excellent drillability and copper foil adhesion, a laminate using the prepreg, a printed circuit board, and a semiconductor package. [Means for solving the problem]

[0008] The present inventors conducted extensive research to solve the above problems and, as a result, found that the above problems can be solved by the following embodiment, and have completed this embodiment. In other words, this embodiment relates to the following [1] to

[11] . [1] A resin composition containing (A) a thermosetting resin and (B) spherical zinc molybdate, and a fiber base material, The basis weight of the aforementioned fiber base material is 50 g / m 2 That's all for the prepreg. [2] The prepreg according to [1] above, wherein the thickness of the fiber base material is 50 μm or more. [3] The prepreg according to [1] or [2] above, wherein the fiber base material is glass cloth. [4] The prepreg according to [3] above, wherein the glass fibers constituting the glass cloth are one or more selected from the group consisting of D glass, T glass, and S glass. [5] The average particle size (D) of the spherical zinc molybdate (B) 50 A prepreg according to any of the above [1] to [4], wherein the diameter is 0.01 to 20 μm. [6] The prepreg according to any one of [1] to [5] above, wherein the content of (B) spherical zinc molybdate in the resin composition is 0.1 to 10% by mass with respect to the total amount of solids (100% by mass) of the resin composition. [7] The prepreg according to any one of [1] to [6] above, wherein the (A) thermosetting resin contains one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of said maleimide resin. [8] The prepreg according to [7], wherein the thermosetting resin (A) further contains an epoxy resin. [9] A laminate having a cured prepreg according to any of [1] to [8] above, and a metal foil.

[10] A printed circuit board having a cured prepreg according to any of [1] to [8] above.

[11] A semiconductor package having the printed circuit board described in

[10] above and a semiconductor element. [Effects of the Invention]

[0009] According to this embodiment, it is possible to provide a prepreg with excellent drillability and copper foil adhesion, a laminate using the prepreg, a printed circuit board, and a semiconductor package. [Modes for carrying out the invention]

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

[0011] Unless otherwise specified, each component and material exemplified herein 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 multiple substances present in the resin composition, unless otherwise specified, if multiple substances corresponding to each component are present in the resin composition.

[0012] In this specification, "solids" means components other than the solvent, and includes liquid, syrup-like, and waxy substances at room temperature. Here, room temperature is defined as 25°C.

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

[0014] In this specification, weight-average molecular weight (Mw) refers to the value measured in polystyrene equivalent 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, "cured product" is synonymous with a resin composition in the C-stage state as defined in JIS K 6800 (2006).

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

[0017] Embodiments that combine any combination of the information described herein are also included.

[0018] [Prepreg] The prepreg of this embodiment is (A) A thermosetting resin and (B) a resin composition containing spherical zinc molybdate, and a fiber base material, The basis weight of the aforementioned fiber base material is 50 g / m2 That's all; it's a prepreg. The components and other details constituting the prepreg of this embodiment will be described in order below.

[0019] [Resin composition] The prepreg of this embodiment contains a resin composition comprising (A) a thermosetting resin and (B) spheroidal zinc molybdate.

[0020] <(A) Thermosetting resin> (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, melamine resins, and the like. (A) The thermosetting resin may be used individually or in combination of two or more types. Among these, (A) as thermosetting resins, maleimide resin, epoxy resin, and cyanate resin are preferred from the viewpoint of heat resistance and copper foil adhesion, and maleimide resin and epoxy resin are more preferred.

[0021] (Maleimide resin) As the maleimide resin, one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of said maleimide resin is preferred. In the following explanation, "one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of said maleimide resins" may be referred to as "maleimide-based resins." Furthermore, in the following explanation, maleimide resins having one or more N-substituted maleimide groups may be referred to as "maleimide resin (AX)" or "(AX) component". Furthermore, in the following explanation, a maleimide resin derivative having one or more N-substituted maleimide groups may be referred to as "maleimide resin derivative (AY)" or "(AY) component."

[0022] -Maleimide resin (AX)- The maleimide resin (AX) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups. 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, from the viewpoint of copper foil adhesion and heat resistance. In this specification, "aromatic maleimide resin" means a compound having an N-substituted maleimide group directly bonded to an aromatic ring. Furthermore, in this specification, "aromatic bismaleimide resin" means a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. Furthermore, in this specification, "aromatic polymaleimide resin" means a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring. Furthermore, in this specification, "aliphatic maleimide resin" means a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0023] As the maleimide resin (AX), a maleimide resin represented by the following general formula (A1-1) [hereinafter referred to as "maleimide resin (A1)"] is preferred.

[0024] [ka] (In the formula, X A11 (It is a divalent organic group.)

[0025] X in the above general formula (A1-1) A11 It is a divalent organic group. X in the above general formula (A1-1) A11 Examples of divalent organic groups represented by include the divalent group represented by the following general formula (A1-2), the divalent group represented by the following general formula (A1-3), the divalent group represented by the following general formula (A1-4), the divalent group represented by the following general formula (A1-5), and the divalent group represented by the following general formula (A1-6).

[0026] [Chemical formula] (In the formula, R A11 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. n A11 is an integer of 0 to 4. * represents a bonding site.)

[0027] Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R A11 in the general formula (A1-2) include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, etc.; alkenyl groups having 2 to 5 carbon atoms; alkynyl groups having 2 to 5 carbon atoms, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom, etc. n A11 in the general formula (A1-2) is an integer of 0 to 4. From the viewpoint of easy availability, it is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. n A11 When n A11 is an integer of 2 or more, the plurality of R

[0028] [Chemical formula] (In the formula, R A12 and R A13 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X A12 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 group represented by the following general formula (A1-3-1). n A12 and n A13 are each independently an integer of 0 to 4. * represents a bonding site.)

[0029] In the above general formula (A1-3), R A12 and R A13 Examples of C1-C5 aliphatic hydrocarbon groups represented by include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. The C1-C5 aliphatic hydrocarbon group is preferably a C1-C3 aliphatic hydrocarbon group, more preferably a C1-C3 alkyl group, and even more preferably a methyl or ethyl group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0030] X in the above general formula (A1-3) A12 Examples of alkylene groups having 1 to 5 carbon atoms include methylene groups, 1,2-dimethylene groups, 1,3-trimethylene groups, 1,4-tetramethylene groups, and 1,5-pentamethylene groups. Among the alkylene groups having 1 to 5 carbon atoms, alkylene groups having 1 to 3 carbon atoms are preferred, alkylene groups having 1 or 2 carbon atoms are more preferred, and methylene groups are even more preferred.

[0031] X in the above general formula (A1-3) A12 Examples of alkylidene groups having 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butyridene, isobutylidene, pentyridene, and isopentylidene. Among these, alkylidene groups having 2 to 4 carbon atoms are preferred, alkylidene groups having 2 or 3 carbon atoms are more preferred, and isopropylidene groups are even more preferred.

[0032] n in the above general formula (A1-3) A12 and n A13 Each of these is an integer between 0 and 4, independently of the others. n A12 or n A13 If is an integer greater than or equal to 2, then multiple RA12 Each or multiple R A13 They may be the same or they may be different.

[0033] X in the above general formula (A1-3) A12 The divalent group represented by the general formula (A1-3-1) is as follows:

[0034] [ka] (In the formula, R A14 and R A15 Each of these is independently an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. A13 This 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. A14 and n A15 Each of these is an independent integer between 0 and 4. * represents a connection point.

[0035] In the above general formula (A1-3-1), R A14 and R A15 Examples of C1-C5 aliphatic hydrocarbon groups represented by include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0036] X in the above general formula (A1-3-1) A13Examples of alkylene groups having 1 to 5 carbon atoms include methylene groups, 1,2-dimethylene groups, 1,3-trimethylene groups, 1,4-tetramethylene groups, and 1,5-pentamethylene groups. Among the alkylene groups having 1 to 5 carbon atoms, alkylene groups having 1 to 3 carbon atoms are preferred, alkylene groups having 1 or 2 carbon atoms are more preferred, and methylene groups are even more preferred.

[0037] X in the above general formula (A1-3-1) A13 Examples of alkylidene groups having 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butyridene, isobutylidene, pentyridene, and isopentylidene. Among these, alkylidene groups having 2 to 4 carbon atoms are preferred, alkylidene groups having 2 or 3 carbon atoms are more preferred, and isopropylidene groups are even more preferred.

[0038] X in the above general formula (A1-3-1) A13 Among the above options, alkylidene groups having 2 to 5 carbon atoms are preferred, alkylidene groups having 2 to 4 carbon atoms are more preferred, and isopropylidene groups are even more preferred.

[0039] n in the above general formula (A1-3-1) A14 and n A15 Each of these is an integer between 0 and 4, and from the viewpoint of availability, each is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0. n A14 or n A15 If is an integer greater than or equal to 2, then multiple R A14 Each or multiple R A15 They may be the same or they may be different.

[0040] X in the above general formula (A1-3) A12 Among the above options, alkylene groups having 1 to 5 carbon atoms, alkylidene groups having 2 to 5 carbon atoms, and divalent groups represented by the above general formula (A1-3-1) are preferred, alkylene groups having 1 to 5 carbon atoms are more preferred, and methylene groups are even more preferred.

[0041] [ka] (In the formula, n A16 (This is an integer between 0 and 10. * represents a connection point.)

[0042] n in the above general formula (A1-4) A16 From the viewpoint of availability, the integer is preferably an integer between 0 and 5, more preferably an integer between 0 and 4, and even more preferably an integer between 0 and 3.

[0043] [ka] (In the formula, n A17 (The numbers are 0-5. * represents a connection site.)

[0044] [ka] (In the formula, R A16 and R A17 Each of these is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. A18 (This is an integer between 1 and 8. * represents a connection point.)

[0045] In the above general formula (A1-6), R A16 and R A17 Examples of C1-C5 aliphatic hydrocarbon groups represented by include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. n in the above general formula (A1-6) A18 n is an integer between 1 and 8, preferably between 1 and 5, more preferably between 1 and 3, and even more preferably 1. A18 If is an integer greater than or equal to 2, then multiple R A16Each or multiple R A17 They may be the same or they may be different.

[0046] Examples of maleimide resins (A1) include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins. Specific examples of maleimide resin (A1) include N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl- 4,4'-Diphenylmethanebismaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-male (imidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-Bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, bis(4-maleimidophenoxy)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide Rufoxide, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl [L]benzene, 1,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3- Examples include bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethanemaleimide, and biphenyl aralkyl maleimide. Among these, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane is preferred.

[0047] -Maleimide resin derivative (AY)- As the maleimide resin derivative (AY), a resin having a structure derived from the above-mentioned maleimide resin (AX) and a structure derived from a diamine compound [hereinafter, this may be referred to as "aminomaleimide resin (A2)" or "component (A2)"] is preferred.

[0048] -Aminomaleimide resin (A2)- The aminomaleimide resin (A2) has a structure derived from the maleimide resin (AX) and a structure derived from the diamine compound.

[0049] Structure derived from maleimide resin (AX) Examples of structures derived from maleimide resin (AX) include structures in which at least one N-substituted maleimide group of the maleimide resin (AX) undergoes a Michael addition reaction with an amino group of a diamine compound. The structure derived from maleimide resin (AX) contained in aminomaleimide resin (A2) may be a single type or two or more types.

[0050] The content of structures derived from maleimide resin (AX) in aminomaleimide resin (A2) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and even more preferably 60 to 90% by mass. When the content of structures derived from maleimide resin (AX) in aminomaleimide resin (A2) is within the above range, dielectric properties and handling properties when used as a resin film tend to be better.

[0051] Structure derived from diamine compounds Examples of structures derived from diamine compounds include structures formed by a Michael addition reaction between one or both of the two amino groups of the diamine compound and an N-substituted maleimide group of the maleimide resin (AX). The structure derived from the diamine compound contained in the aminomaleimide resin (A2) may be a single type or two or more types.

[0052] The amino group in the diamine compound is preferably a primary amino group. Examples of structures derived from diamine compounds having two primary amino groups include the group represented by the following general formula (A2-1) and the group represented by the following general formula (A2-2).

[0053] [ka] (In the formula, X A21 (where * represents a divalent organic group, and * represents a bonding site.)

[0054] X in the above general formula (A2-1) and the above general formula (A2-2) A21 It is a divalent organic group, corresponding to a divalent group obtained by removing two primary amino groups from a diamine compound.

[0055] X in the above general formula (A2-1) and the above general formula (A2-2) A21 It is preferable that the group is a divalent group represented by the following general formula (A2-3).

[0056] [ka] (In the formula, R A21 and R A22 Each of these is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. A22 This refers to 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 fluorenylene group, a single bond, or a divalent group represented by the following general formula (A2-3-1) or (A2-3-2). A21 and n A22 Each of these is an independent integer between 0 and 4. * represents a connection point.

[0057] [ka] (In the formula, R A23 and R A24 Each of these is independently an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. A23This is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. A23 and n A24 Each of these is an independent integer between 0 and 4. * represents a connection point.

[0058] [ka] (In the formula, R A25 X is an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. A24 and X A25 Each of these is independently 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. A25 (This is an integer between 0 and 4. * represents a connection site.)

[0059] In the above general formulas (A2-3), (A2-3-1), and (A2-3-2), R A21 , R A22 , R A23 , R A24 and R A25 Examples of C1-C5 aliphatic hydrocarbon groups represented by include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. The C1-C5 aliphatic hydrocarbon group is preferably a C1-C3 aliphatic hydrocarbon group, more preferably a C1-C3 alkyl group, and even more preferably a methyl or ethyl group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0060] X in the above general formula (A2-3) A22X in the general formula (A2-3-1) above A23 and X in the general formula (A2-3-2) above A24 and X A25 The alkylene group having 1 to 5 carbon atoms represented by may include, for example, a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, and the like. As the alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and a methylene group is even more preferable.

[0061] X in the general formula (A2-3) above A22 X in the general formula (A2-3-1) above A23 and X in the general formula (A2-3-2) above A24 and X A25 The alkylidene group having 2 to 5 carbon atoms represented by may include, for example, an ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. As the alkylidene group having 2 to 5 carbon atoms, an alkylidene group having 2 to 4 carbon atoms is preferable, an alkylidene group having 2 or 3 carbon atoms is more preferable, and an isopropylidene group is even more preferable.

[0062] n in the general formula (A2-3) above A21 and n A22 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 2. n A21 or n A22 When is an integer of 2 or more, a plurality of R A21 or a plurality of R A22 may be the same as or different from each other.

[0063] n in the general formula (A2-3-1) above A23 and n A24 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. n A23 or n A24 is an integer of 2 or more, a plurality of R A23 each other or a plurality of R A24 each other may be the same or different from each other.

[0064] n in the general formula (A2-3-2) A25 is an integer from 0 to 4, and from the viewpoint of availability, is preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0. n A25 is an integer of 2 or more, a plurality of R A25 each other may be the same or different from each other.

[0065] Also, X in the general formula (A2-1) and the general formula (A2-2) A21 may be a divalent group containing a structure represented by the following general formula (A2-4), or may be a divalent group represented by the following general formula (A2-5).

[0066]

Chemical formula

[0067]

Chemical formula

[0068] In the above general formulas (A2-4) and (A2-5), R A26 ~R A29 Examples of C1-C5 aliphatic hydrocarbon groups represented by include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. C1-C3 aliphatic hydrocarbon groups are preferred, C1-C3 alkyl groups are more preferred, and methyl groups are even more preferred. R A26 ~R A29 Examples of substituents on the phenyl group in the substituted phenyl group represented by include the aliphatic hydrocarbon groups having 1 to 5 carbon atoms as described above.

[0069] X A26 and X A27 Examples of divalent organic groups represented by include alkylene groups, alkenylene groups, alkynylene groups, arylene groups, -O- groups, or divalent linking groups formed by combinations of these groups. Examples of the alkylene groups mentioned above include alkylene groups having 1 to 10 carbon atoms, such as methylene groups, ethylene groups, and propylene groups. Examples of the above-mentioned alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group mentioned above include alkynylene groups having 2 to 10 carbon atoms. Examples of the above-mentioned arylene groups include phenylene groups, naphthylene groups, and other arylene groups having 6 to 20 carbon atoms. Among these, X A26 and X A27 Of these, alkylene groups and arylene groups are preferred, with alkylene groups being more preferred.

[0070] n A26n is an integer between 2 and 100, preferably between 2 and 50, more preferably between 3 and 40, and even more preferably between 5 and 30. A26 If is an integer greater than or equal to 2, then multiple R A26 Each or multiple R A27 They may be the same or they may be different.

[0071] The content of structures derived from diamine compounds in the aminomaleimide resin (A2) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and even more preferably 10 to 40% by mass. When the content of structures derived from diamine compounds in the aminomaleimide resin (A2) is within the above range, the dielectric properties, heat resistance, flame retardancy, and glass transition temperature tend to be better.

[0072] Examples of diamine compounds include 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, and 3,3'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisanili Examples include aromatic diamine compounds such as 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, and 9,9-bis(4-aminophenyl)fluorene; and silicone compounds having two primary amino groups. In this specification, "aromatic diamine compound" means a compound having two amino groups directly bonded to an aromatic ring.

[0073] Among these, 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, and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred, with 3,3'-diethyl-4,4'-diaminodiphenylmethane being more preferred, from the viewpoint of excellent solubility in organic solvents, reactivity, heat resistance, dielectric properties, and low water absorption. Furthermore, from the viewpoint of low thermal expansion, silicone compounds having two primary amino groups are preferred.

[0074] As a silicone compound having two primary amino groups, a silicone compound having primary amino groups at both ends is preferred. The primary amino group equivalent of a silicone compound having two primary amino groups is not particularly limited, but 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.

[0075] The equivalence ratio (Ta2 / Ta1) of the total equivalent amount of groups derived from the -NH2 group of the diamine compound in the aminomaleimide resin (A2) to the total equivalent amount of groups derived from the N-substituted maleimide group of the maleimide resin (AX) is not particularly limited, but from the viewpoint of dielectric properties, heat resistance, flame retardancy and glass transition temperature, it is preferably 0.05 to 10, more preferably 1 to 8, and even more preferably 3 to 7. The groups derived from the -NH2 group of the diamine compound include the -NH2 group itself. The groups derived from the N-substituted maleimide group of the maleimide resin (AX) also include the N-substituted maleimide group itself.

[0076] The weight-average molecular weight (Mw) of the aminomaleimide resin (A2) is not particularly limited, but from the viewpoint of handling and moldability, it is preferably 400 to 10,000, more preferably 1,000 to 5,000, even more preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000.

[0077] The aminomaleimide resin (A2) can be produced, for example, by reacting a maleimide resin (AX) with a diamine compound in an organic solvent. By reacting maleimide resin (AX) with a diamine compound, an aminomaleimide resin (A2) is obtained through a Michael addition reaction between the maleimide resin (AX) and the diamine compound. When reacting maleimide resin (AX) with a diamine compound, a reaction catalyst may be used as needed.

[0078] The reaction temperature for the Michael addition reaction is preferably 50 to 160°C, more preferably 60 to 150°C, and even more preferably 70 to 140°C, from the viewpoint of workability such as reaction rate and suppression of product gelation during the reaction. The reaction time for the Michael addition reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and even more preferably 2 to 6 hours, from the viewpoint of productivity and ensuring the reaction proceeds sufficiently. However, these reaction conditions can be adjusted as appropriate depending on the type of raw materials used, and are not particularly limited.

[0079] (Epoxy resin) The epoxy resin is preferably an epoxy resin having two or more epoxy groups. Epoxy resins are classified into, for example, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxy resins. Among these, glycidyl ether type epoxy resins are preferred.

[0080] Epoxy resins are classified into various types based on differences in their main structural framework. Specifically, epoxy resins are classified into categories such as: bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; novolac-type epoxy resins such as bisphenol A novolac-type epoxy resin, bisphenol F novolac-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, biphenyl novolac-type epoxy resin, and naphthol novolac-type epoxy resin; aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, and naphthol aralkyl-type epoxy resin; stilbene-type epoxy resin; naphthylene ether-type epoxy resin; biphenyl-type epoxy resin; dihydroanthracene-type epoxy resin; epoxy resins containing a saturated dicyclopentadiene skeleton; cyclohexanedimethanol-type epoxy resin; spiro-ring-containing epoxy resin; heterocyclic epoxy resin; alicyclic epoxy resin; aliphatic chain-type epoxy resin; and rubber-modified epoxy resin. Among these, epoxy resins containing a biphenyl structure are preferred, and biphenyl aralkyl-type epoxy resins are more preferred.

[0081] The resin composition of this embodiment preferably contains (A) one or more thermosetting resins selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of said maleimide resins, and more preferably contains an epoxy resin. (A) The content of one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of said maleimide resins in the thermosetting resin is not particularly limited, but is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 70 to 85% by mass. (A) The content of epoxy resin in the thermosetting resin is not particularly limited, but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass.

[0082] In the resin composition of this embodiment, the content of (A) thermosetting resin is not particularly limited, but is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 80 to 100% by mass, relative to the total amount (100% by mass) of resin components in the resin composition of this embodiment. (A) When the thermosetting resin content is within the above range, heat resistance, moldability, processability, and copper foil adhesion tend to be better.

[0083] Herein, in this specification, "resin component" means resin and compounds that form resin through a curing reaction. However, (D) curing accelerators are not included in the resin component.

[0084] The content of the resin component in the resin composition of this embodiment is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 50% by mass, relative to the total solid content (100% by mass) of the resin composition of this embodiment. When the resin component content is above the lower limit, heat resistance, moldability, processability, and copper foil adhesion tend to be better. Conversely, when the resin component content is below the upper limit, low thermal expansion tend to be better.

[0085] <(B) Spheroidal zinc molybdate> The prepreg of this embodiment, by containing (B) spherical zinc molybdate in its resin composition, exhibits not only excellent drillability but also superior copper foil adhesion. The reason why the prepreg of this embodiment has superior copper foil adhesion is not entirely clear, but it is presumed that (B) spherical zinc molybdate has the effect of homogenizing the surface of the prepreg, thereby improving the adhesion between the prepreg and the copper foil. In this embodiment, zinc molybdate is a salt of molybdic acid and zinc, and its chemical formula is, for example, Zn X Mo Y O4(0.5 <X<2.5、0.5<Y<2.5)、Zn X Mo Y O4(OH) ZIt is represented by (0.5 < X < 2.5, 0.5 < Y < 2.5, 0.5 < Z < 2.5), etc.

[0086] Also, in this embodiment, "spherical" means that the circularity calculated by the following formula is 90 or more, using the area and perimeter measured from a photograph of the target particles. Circularity = {4π × (area) ÷ (perimeter) 2} × 100 The closer the circularity is to 100, the closer it is to a perfect sphere. The circularity of the (B) spherical zinc molybdate in this embodiment is preferably 90 - 100, more preferably 93 - 100, still more preferably 95 - 100 from the viewpoint of copper foil adhesion. A more specific method for measuring the circularity is as described in the examples.

[0087] (B) The average particle diameter (D 50 ) of spherical zinc molybdate is not particularly limited, but from the viewpoint of copper foil adhesion, it is preferably 0.01 - 20 μm, more preferably 0.1 - 10 μm, still more preferably 0.2 - 5 μm, and particularly preferably 0.5 - 1.5 μm. In this specification, the average particle diameter (D 50 ) of the particles is the particle diameter at the point corresponding to 50% volume when a cumulative frequency distribution curve by particle diameter is obtained with the total volume of the particles as 100%. The average particle diameter (D 50 ) can be measured, for example, with a particle size distribution measuring device using the laser diffraction scattering method. <http: / / www.example.com> In the resin composition of this embodiment, the content of (B) spherical zinc molybdate is not particularly limited, but is preferably 0.1 - 10% by mass, more preferably 0.2 - 7% by mass, still more preferably 0.5 - 5% by mass with respect to the total solid content (100% by mass) of the resin composition. When the content of (B) spherical zinc molybdate is within the above range, the drillability and copper foil adhesion tend to be better.

[0089] <(C) Inorganic filler> The resin composition of this embodiment preferably further contains (C) an inorganic filler. The resin composition of this embodiment tends to exhibit better low thermal expansion and heat resistance by containing (C) an inorganic filler. In this embodiment, (B) spheroidal zinc molybdate is not included in the concept of (C) inorganic filler. (C) Inorganic fillers may be used individually or in combination of two or more types.

[0090] (C) Examples of inorganic fillers include silica, alumina, titanium oxide, mica, beryllium, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, etc. 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.

[0091] Examples of silica include precipitated silica with a high water content produced by a wet process, and dry-process silica that contains almost no bound water, etc., produced by a dry process. Dry-process silica can be further categorized into crushed silica, fumed silica, fused silica, etc., depending on the manufacturing method. Among these, fused silica is preferred from the viewpoint of dispersibility and moldability.

[0092] (C) Average particle size of inorganic filler (D 50 (C) is not particularly limited, but from the viewpoint of dispersibility and fine wiring properties of the inorganic filler, it is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, even more preferably 0.2 to 5 μm, and especially preferably 0.3 to 2 μm. (C) Examples of inorganic filler shapes include spherical and crushed forms, with spherical being preferred.

[0093] The resin composition of this embodiment may contain a coupling agent for the purpose of improving the dispersibility of (C) the inorganic filler and the adhesion between (C) the inorganic filler and the organic component. Examples of coupling agents include silane coupling agents and titanate coupling agents. Among these, silane coupling agents are preferred.

[0094] If the resin composition of this embodiment contains (C) an inorganic filler, the amount of (C) an inorganic filler is not particularly limited, but is preferably 10 to 80% by mass, more preferably 30 to 75% by mass, even more preferably 40 to 70% by mass, even more preferably 50 to 67% by mass, and most preferably 55 to 65% by mass, relative to the total amount of solids (100% by mass) of the resin composition. (C) When the inorganic filler content is above the lower limit, the low thermal expansion and heat resistance tend to be better. Also, when the inorganic filler content is below the upper limit, the moldability and copper foil adhesion tend to be better.

[0095] <(D) Curing accelerator> The resin composition of this embodiment preferably further contains (D) a curing accelerator. The resin composition of this embodiment tends to have improved curability and better copper foil adhesion due to the inclusion of (D) a curing accelerator. (D) The curing accelerator may be used alone or in combination of two or more types.

[0096] (D) Examples of curing accelerators include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, tributylamine, pyridine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate; isocyanate mask imidazole compounds such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; organic peroxides such as 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'-bis(t-butylperoxy)diisopropylbenzene; and carboxylates of manganese, cobalt, zinc, etc. Among these, isocyanate maximidazole compounds are preferred from the viewpoint of curing acceleration effect and storage stability.

[0097] If the resin composition of this embodiment contains (D) a curing accelerator, the amount of (D) the curing accelerator is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of (A) the thermosetting resin. (D) When the content of the curing accelerator is above the lower limit above, a sufficient curing acceleration effect tends to be easily obtained. Also, when the content of the curing accelerator is below the upper limit above, storage stability tends to be better.

[0098] <Other optional ingredients> The resin composition of this embodiment may further contain, if necessary, one or more other optional components selected from the group consisting of resin materials other than the above-mentioned components, flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, organic solvents, and other additives. Each of the above optional components may be used individually or in combination of two or more. The content of the above-mentioned 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 this embodiment may not contain the above-mentioned optional components, depending on the desired performance.

[0099] (organic solvent) The resin composition of this embodiment may contain an organic solvent from the viewpoint of facilitating handling and facilitating the manufacture of prepregs. Organic solvents may be used individually or in combination of two or more. In this specification, a resin composition containing an organic solvent may be referred to as a resin varnish.

[0100] Examples of organic solvents include alcoholic solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic hydrocarbon 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 solvents such as γ-butyrolactone. Among these, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, nitrogen atom-containing solvents, and aromatic hydrocarbon-based solvents are preferred, aromatic hydrocarbon-based solvents are more preferred, and toluene is even more preferred.

[0101] <Method for producing resin compositions> The resin composition of this embodiment can be manufactured by mixing each component. In this process, each component may be dissolved or dispersed while stirring. The mixing order, temperature, time, and other conditions are not particularly limited and can be set arbitrarily according to the type of raw materials, etc.

[0102] [Textile base material] The basis weight of the fibrous base material contained in the prepreg of this embodiment is 50 g / m². 2 That's all. The basis weight of the fiber base material is 50g / m 2 As a result of the above, the prepreg of this embodiment has excellent mechanical strength. From the viewpoint of the mechanical strength of the prepreg, the basis weight of the fiber base material is preferably 60 g / m². 2 Above, a comfortable 70g / m 2 More preferably 80 g / m² 2 The above conditions are met, and from the viewpoint of high-density wiring, 150 g / m² is preferred. 2 More preferably, 140 g / m² 2 More preferably, 130 g / m² 2 The following is particularly preferred: 120 g / m² 2 The following applies: From the viewpoint of mechanical strength and high-density wiring of the prepreg, the basis weight of the fiber base material is preferably 50 to 150 g / m². 2 , more preferably 60-140 g / m² 2 More preferably 70-130 g / m² 2 Particularly preferred is 80-120 g / m² 2 That is the case.

[0103] The thickness of the fiber base material is preferably 50 μm or more, more preferably 60 μm or more, even more preferably 70 μm or more, and particularly preferably 80 μm or more, from the viewpoint of the mechanical strength of the prepreg, and preferably 150 μm or less, more preferably 140 μm or less, even more preferably 130 μm or less, and particularly preferably 120 μm or less, from the viewpoint of high-density wiring. The thickness of the fibrous substrate is not particularly limited, but from the viewpoint of the mechanical strength of the prepreg and high-density wiring, it is preferably 50 to 150 μm, more preferably 60 to 140 μm, even more preferably 70 to 130 μm, and especially preferably 80 to 120 μm.

[0104] The fibrous base material may take the form of, for example, woven fabric, nonwoven fabric, robbing, chopped strand mat, or surfacing mat. The fibrous base material may be surface-treated with a coupling agent or mechanically opened, from the viewpoint of impregnation properties of the resin composition.

[0105] Examples of fibers constituting the fibrous base material include inorganic fibers such as glass fibers; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. Among these, inorganic fibers are preferred from the viewpoint of low thermal expansion, and glass fibers are more preferred. From a similar viewpoint, the fibrous base material is preferably glass cloth.

[0106] Examples of glass fibers include E-glass, D-glass, T-glass, and S-glass. Among these, from the viewpoint of low thermal expansion, one or more selected from the group consisting of D-glass, T-glass, and S-glass are preferred. The typical compositions of E glass, D glass, T glass, and S glass are as follows: ·E glass: SiO2 (52~56 mass%), Al2O3 (12~16 mass%), Fe2O3 (0~0.8 mass%), B2O3 (5~10 mass%), CaO (16~25 mass%), MgO (0~6 mass%), Na2O+K2O (0~2 mass%), TiO2 (0~1.5 mass%), F2 (0~1 mass%) ·D glass: SiO2 (74 mass%), Al2O3 (0.5 mass%), B2O3 (22 mass%), CaO (0.5 mass%), Na2O (1 mass%), K2O (1.5 mass%), Li2O (0.5 mass%), ·T glass: SiO2 (64~66% by mass), Al2O3 (24~26% by mass), MgO (9~11% by mass) S glass: SiO2 (62-65% by mass), Al2O3 (20-25% by mass), CaO (0-0.01% by mass), MgO (10-15% by mass), B2O3 (0-0.01% by mass), Na2O and K2O (0-1% by mass)

[0107] The SiO2 content in the glass fibers is not particularly limited, but is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, even more preferably 50 to 80% by mass, and especially preferably 60 to 75% by mass. When the SiO2 content in the glass fibers is above the lower limit, the prepreg tends to exhibit excellent low thermal expansion and low warping properties. Conversely, when the SiO2 content in the glass fibers is below the upper limit, the prepreg tends to have better drillability.

[0108] [Prepreg manufacturing method] The prepreg of this embodiment can be manufactured, for example, by impregnating a fibrous substrate with a resin composition and then B-stage the resin composition.

[0109] Methods for impregnating a fiber substrate with a resin composition include, for example, the hot melt method and the solvent method.

[0110] The hot melt method is a method of impregnating a fibrous substrate with a resin composition that does not contain organic solvents. One embodiment of the hot melt method involves first coating a coated paper with good release properties with the resin composition of this embodiment, which does not contain an organic solvent, and then impregnating a fibrous substrate by laminating the coated resin composition onto it. Another aspect of the hot melt method is a method in which the resin composition of this embodiment, which does not contain an organic solvent, is directly applied to a fibrous substrate using a die coater or the like to impregnate it.

[0111] The solvent method is a method of impregnating a fiber substrate with a resin composition containing an organic solvent. Specifically, for example, one method involves immersing the fiber substrate in the resin composition of this embodiment containing an organic solvent, then drying it to remove the organic solvent and to B-stage the resin composition. The drying temperature is not particularly limited, but from the viewpoint of productivity and moderately B-staging the resin composition, it is preferably 50 to 200°C, more preferably 100 to 190°C, and even more preferably 150 to 180°C. The drying time is not particularly limited, but from the viewpoint of productivity and moderately B-staging the resin composition, it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and even more preferably 3 to 10 minutes.

[0112] The content of the resin composition in the prepreg of this embodiment is not particularly limited, but from the viewpoint of moldability, it is preferably 30 to 80% by mass, more preferably 35 to 70% by mass, and even more preferably 40 to 60% by mass.

[0113] [Laminated board] The laminate of this embodiment is a laminate having a cured prepreg of this embodiment and a metal foil. Laminates containing metal foil are sometimes referred to as metal-clad laminates.

[0114] The metal used in the metal foil is not particularly limited and includes, for example, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metallic elements.

[0115] The laminate of this embodiment can be manufactured, for example, by placing metal foil on one or both sides of the prepreg of this embodiment and then heat-pressure molding it. Typically, this heat-pressure molding process is used to cure the B-staged prepreg, thereby obtaining the laminate of this embodiment. When performing heat and pressure molding, one prepreg sheet may be used, or two or more prepreg sheets may be laminated together. For heat and pressure molding, for example, multi-stage presses, multi-stage vacuum presses, continuous molding machines, autoclave molding machines, etc., can be used. The conditions for heat-pressure molding are not particularly limited, but for example, the temperature can be 100-300°C, the time 10-300 minutes, and the pressure 1.5-5 MPa.

[0116] [Printed wiring board] The printed circuit board of this embodiment is a printed circuit board having a cured prepreg of this embodiment. The printed circuit board of this embodiment can be manufactured, for example, by forming conductive circuits on a cured prepreg of this embodiment using a known method. Furthermore, a multilayer printed circuit board can be manufactured by performing a multilayer bonding process as needed. Conductor circuits can be formed by, for example, drilling holes, metal plating, etching metal foil, etc., as appropriate.

[0117] [Semiconductor Packages] The semiconductor package of this embodiment is a semiconductor package having the printed circuit board of this embodiment and semiconductor elements. The semiconductor package of this embodiment can be manufactured, for example, by mounting a semiconductor chip, memory, etc., on the printed circuit board of this embodiment using a known method. [Examples]

[0118] The embodiment will be described in detail below with reference to examples. However, this embodiment is not limited to the following examples.

[0119] In each example, the weight-average molecular weight (Mw) was measured by the following method. The results were calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a cubic equation using standard polystyrene: TSKstandard POLYSTYRENE (Type; 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. Device: Pump: L-6200 model [manufactured by Hitachi High-Technologies Corporation] Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation] Column Oven: L-655A-52 [Manufactured by Hitachi High-Technologies Corporation] Columns: Guard column; TSK Guardcolumn HHR-L+; TSKgel G4000HHR+TSKgel G2000HHR (all manufactured by Tosoh Corporation, product names) Column sizes: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column) Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL Injection volume: 20μL Flow rate: 1.00mL / min Measurement temperature: 40℃

[0120] Manufacturing Example 1: Production of aminomaleimide resin In a 5-liter reaction vessel capable of heating and cooling, equipped with a thermometer, stirrer, and moisture meter with reflux condenser, 100 parts by mass of 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 5.6 parts by mass of a silicone compound having primary amino groups at both ends (primary amino group equivalent 750 g / mol), 7.9 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 171 parts by mass of propylene glycol monomethyl ether were added and reacted under reflux for 2 hours. This was concentrated at reflux temperature over 3 hours to produce a solution of aminomaleimide resin with a solid content of 65% by mass. The weight-average molecular weight (Mw) of the obtained aminomaleimide resin was approximately 2,700.

[0121] [Method for measuring circularity] Using a scanning electron microscope (SEM) (JEOL Ltd., product name "JSM-6010PLUS / LA"), zinc molybdate was observed at 5,000x magnification, and the area and perimeter of 10 arbitrary particles were measured in the resulting SEM images. Next, using the obtained area and perimeter, the circularity of each particle was calculated based on the following formula, and the average of these values ​​was used as the circularity of the zinc molybdate used in each example. Roundness = {4π × (area) ÷ (perimeter)} 2}×100

[0122] Examples 1-2, Comparative Examples 1-2 (Manufacturing of resin compositions) Each component listed in Table 1 was stirred and mixed with methyl ethyl ketone to prepare a varnish-like resin composition with a solid content concentration of 60% by mass. In Table 1, the unit of the amount of each component is parts by mass, and in the case of a solution, it means parts by mass on a solid content basis.

[0123] (Prepreg manufacturing) The varnish-like resin composition obtained above is applied to glass cloth (basis weight: 114 g / m²). 2 A prepreg was obtained by impregnating glass (type: T glass, glass cloth thickness: 98 μm) with the material and heating and drying it at 120°C for 3 minutes. The resin composition content in the prepreg was 50% by mass.

[0124] (Manufacturing of copper-clad laminates) Seven sheets of the prepreg obtained above were stacked, and 12 μm thick copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-M3-VLP-12", Rz: 3.0 μm of the M-side (roughened surface)) was placed above and below it so that the M-side (roughened surface) was in contact with the prepreg. This laminate was heated and pressurized for 90 minutes at a temperature of 240°C and a pressure of 3.0 MPa to obtain a copper-clad laminate.

[0125] [Evaluation Method] Each evaluation was conducted according to the method described below. The results are shown in Table 1.

[0126] (Method for measuring drill hole misalignment) Three layers of copper-clad laminate were stacked, with a 0.15mm thick aluminum foil on top and a 1.5mm thick paper phenolic board underneath. Next, 10,000 holes were drilled using a φ0.15mm drill bit with a drilling machine (manufactured by Via Mechanics Co., Ltd., product name "ND-1V212") under the conditions of a rotation speed of 200krpm, a feed rate of 2m / min, and a chip load of 10μm / rev. The misalignment of the holes on the bottom side (drill exit side) of the third layer of the three-layered copper-clad laminate was measured using a hole position accuracy measuring instrument (manufactured by Via Mechanics Co., Ltd., product name "HT-1AM"), and the average misalignment of 10,000 holes + 3σ (σ: standard deviation) was calculated and used as an indicator of drill hole position accuracy.

[0127] (Method for measuring copper foil peel strength) The copper foil from the copper-clad laminate prepared as described above was etched into 5mm wide straight lines to form test specimens. The formed straight lines of copper foil were mounted on a small benchtop testing machine (manufactured by Shimadzu Corporation, product name "EZ-TEST"), and the copper foil peel strength was measured by peeling it off at a 90° angle at room temperature (25°C). The pulling speed when peeling the copper foil was set to 50mm / min.

[0128] [Table 1]

[0129] The details of each component shown in Table 1 are as follows: [(A) component] • Thermosetting resin 1: Aminomaleimide resin prepared in Production Example 1 • Thermosetting resin 2: Biphenyl aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., "NC-3000", epoxy equivalent 275 g / eq

[0130] [(B) Component] • Spherical zinc molybdate: Average particle size (D 50 0.9 μm, circularity 99

[0131] [Comparison Ingredients] • Zinc molybdate-supported talc: flake-like, less than 90 degrees of roundness, 20% by mass of zinc molybdate supported.

[0132] [(C) component] • Fused silica: Average particle size (D 50 ) 0.5 μm, spherical fused silica

[0133] [(D) component] • Curing accelerator: Isocyanate maskimidazole, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "G-8009L"

[0134] Table 1 shows that the prepregs of Examples 1 and 2 of this embodiment, compared to the prepreg of Comparative Example 1 which does not contain (B) spherical zinc molybdate, are able to reduce the amount of drill hole misalignment while maintaining copper foil peel strength. On the other hand, the prepreg of Comparative Example 2 which contains zinc molybdate-supported talc instead of (B) spherical zinc molybdate, was able to reduce the amount of drill hole misalignment, but the copper foil peel strength was significantly reduced.

Claims

1. (A) A thermosetting resin and (B) a resin composition containing spheroidal zinc molybdate, and a fiber base material, The basis weight of the aforementioned fiber base material is 50 g / m ２ That's all for the prepreg.

2. The prepreg according to claim 1, wherein the thickness of the fibrous substrate is 50 μm or more.

3. The prepreg according to claim 1 or 2, wherein the fibrous base material is glass cloth.

4. The prepreg according to claim 3, wherein the glass fibers constituting the glass cloth are one or more selected from the group consisting of D glass, T glass, and S glass.

5. (B) The average particle size of spherical zinc molybdate (D ５０ The prepreg according to claim 1 or 2, wherein the diameter is 0.01 to 20 μm.

6. The prepreg according to claim 1 or 2, wherein the content of (B) spherical zinc molybdate in the resin composition is 0.1 to 10% by mass with respect to the total solid content (100% by mass) of the resin composition.

7. The prepreg according to claim 1 or 2, wherein the (A) thermosetting resin contains one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of said maleimide resins.

8. The prepreg according to claim 7, wherein the thermosetting resin (A) further contains an epoxy resin.

9. A laminate having a cured prepreg according to claim 1 or 2 and a metal foil.

10. A printed circuit board having a cured prepreg according to claim 1 or 2.

11. A semiconductor package having a printed circuit board according to claim 10 and a semiconductor element.

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