Prepreg, laminate, printed wiring board, and semiconductor package

Abstract

The present invention relates to a prepreg containing a resin composition and a fiber base material, the resin composition containing (A) a thermosetting resin and (B) spherical zinc molybdate, and the weight per unit area of the fiber base material being 50 g / m2 or more, and a laminate, a printed wiring board and a semiconductor package using the prepreg.

Description

Technical Field

[0001] The present embodiment relates to a prepreg, a laminate, a printed wiring board, and a semiconductor package. Background Art

[0002] In recent years, there has been an increasing demand for miniaturization, weight reduction, higher wiring density, and faster processing speeds of printed wiring boards used in electronic devices, communication devices, etc. In response, higher reliability than ever is being demanded for the insulation layer of the printed wiring board.

[0003] As an insulating material for a printed wiring board, a prepreg obtained by impregnating a fiber substrate such as glass cloth with a resin composition is used. In the manufacturing process of the printed wiring board, the cured product of the prepreg is sometimes drilled, and particularly when the fiber substrate has a large weight per unit area, the drill processability is sometimes deteriorated, such as a decrease in the drilling position accuracy due to the hardness of the fiber substrate.

[0004] In recent years, in order to reduce the thermal expansion coefficient of the insulating layer, a high filling of an inorganic filler or a harder fiber base material may be used. In such a case, the deterioration of the drill processability becomes more significant.

[0005] As a method for improving the drill processability of a resin composition, a technique of blending zinc molybdate in a resin composition is known. Patent Document 1 discloses a resin composition containing a molybdenum compound supported on inorganic particles.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2019-199562 Summary of the invention

[0009] Problems to be solved by the invention

[0010] However, studies by the present inventors have revealed that a prepreg formed using a resin composition containing a molybdenum compound supported on inorganic particles has poor adhesion to copper foil (hereinafter also referred to as "copper foil adhesion").

[0011] In view of such a current situation, an object of the present embodiment is to provide a prepreg having excellent drill processability and copper foil adhesion, and a laminate, a printed wiring board, and a semiconductor package using the prepreg.

[0012] Means for solving problems

[0013] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by the present embodiment described below, thereby completing the present embodiment.

[0014] That is, this embodiment relates to the following [1] to

[11] .

[0015] [1] A prepreg comprising a resin composition and a fiber base material, wherein the resin composition comprises (A) a thermosetting resin and (B) spherical zinc molybdate,

[0016] The fiber base material has a unit area weight of 50 g / m 2 above.

[0017] [2] The prepreg according to [1] above, wherein the fiber base material has a thickness of 50 μm or more.

[0018] [3] The prepreg according to [1] or [2] above, wherein the fiber substrate is glass cloth.

[0019] [4] The prepreg according to [3] above, wherein the glass fiber constituting the glass cloth is at least one selected from the group consisting of D glass, T glass and S glass.

[0020] [5] The prepreg according to any one of [1] to [4], wherein the average particle size (D 50 ) is 0.01~20μm.

[0021] [6] The prepreg according to any one of [1] to [5], wherein the content of the spherical zinc molybdate (B) in the resin composition is 0.1 to 10% by mass relative to the total solid content (100% by mass) of the resin composition.

[0022] [7] A prepreg according to any one of [1] to [6] above, wherein the thermosetting resin (A) comprises one or more selected from a maleimide resin having one or more N-substituted maleimide groups and a derivative of the maleimide resin.

[0023] [8] The prepreg according to [7] above, wherein the thermosetting resin (A) further contains an epoxy resin.

[0024] [9] A laminate comprising a cured product of the prepreg according to any one of [1] to [8] above and a metal foil.

[0025]

[10] A printed wiring board comprising a cured product of the prepreg according to any one of [1] to [8] above.

[0026]

[11] A semiconductor package comprising the printed wiring board described in

[10] above and a semiconductor element.

[0027] Effects of the Invention

[0028] According to the present embodiment, it is possible to provide a prepreg having excellent drill processability and copper foil adhesion, and a laminated board, a printed wiring board, and a semiconductor package using the prepreg. DETAILED DESCRIPTION

[0029] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the minimum value and the maximum value, respectively.

[0030] For example, a numerical range such as "X to Y" (X, Y are real numbers) refers to a numerical range greater than X and less than Y. Also, a description such as "greater than X" in this specification refers to X and a numerical value greater than X. In addition, a description such as "less than Y" in this specification refers to Y and a numerical value less than Y.

[0031] The lower limit and upper limit of the numerical range described in the present specification may be arbitrarily combined with the lower limit or upper limit of other numerical ranges, respectively.

[0032] In the numerical range described in the present specification, the lower limit value or the upper limit value of the numerical range may be replaced with the value shown in the Examples.

[0033] Unless otherwise specified, each component and material exemplified in the present specification may be used alone or in combination of two or more.

[0034] In the present specification, when there are plural substances corresponding to each component in the resin composition, the content of each component in the resin composition refers to the total amount of the plural substances present in the resin composition unless otherwise specified.

[0035] In this specification, "solid content" refers to components other than the solvent, and also includes substances that are liquid, syrupy, and waxy at room temperature. Here, in this specification, room temperature means 25°C.

[0036] The expression "containing XX" described in the present specification includes two meanings: containing XX in a state where XX is reacted when XX is capable of reacting, and simply containing XX.

[0037] The weight average molecular weight (Mw) in this specification refers to a value measured by gel permeation chromatography (GPC) and converted to polystyrene. Specifically, the weight average molecular weight (Mw) in this specification can be measured by the method described in Examples.

[0038] The "cured product" in this specification has the same meaning as the resin composition in a C-stage state in JIS K 6800 (2006).

[0039] The mechanism of action described in this specification is a speculation and does not limit the mechanism by which the effects of the present embodiment are achieved.

[0040] Any combination of the matters described in this specification is also included in this embodiment.

[0041] [Prepreg]

[0042] The prepreg of this embodiment includes a resin composition and a fiber base material. The resin composition includes (A) a thermosetting resin and (B) spherical zinc molybdate.

[0043] The fiber base material has a unit area weight of 50 g / m 2 above.

[0044] Hereinafter, components and the like constituting the prepreg according to the present embodiment will be described in order.

[0045] [Resin composition]

[0046] The prepreg of the present embodiment contains a resin composition containing (A) a thermosetting resin and (B) spherical zinc molybdate.

[0047] <(A) Thermosetting resin>

[0048] (A) Thermosetting resins include, for example, 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.

[0049] (A) Thermosetting resins may be used alone or in combination of two or more.

[0050] Among them, as the (A) thermosetting resin, 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.

[0051] (Maleimide resin)

[0052] The maleimide resin is preferably one or more selected from a maleimide resin having one or more N-substituted maleimide groups and a derivative of the maleimide resin.

[0053] In the following description, “one or more selected from a maleimide resin having one or more N-substituted maleimide groups and a derivative of the maleimide resin” may be referred to as “maleimide-based resin”.

[0054] 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 a "component (AX)".

[0055] In the following description, 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 a "(AY) component".

[0056] -Maleimide resin (AX)-

[0057] The maleimide resin (AX) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups.

[0058] From the viewpoint of copper foil adhesion and heat resistance, 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.

[0059] In addition, in this specification, "aromatic maleimide resin" means a compound having an N-substituted maleimide group directly bonded to an aromatic ring.

[0060] In addition, in this specification, "aromatic bismaleimide resin" means a compound having two N-substituted maleimide groups directly bonded to an aromatic ring.

[0061] 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.

[0062] In addition, in this specification, "aliphatic maleimide resin" means a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0063] 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.

[0064] [Chemical formula 1]

[0065]

[0066] (Where X A11 is a divalent organic group.)

[0067] X in the above general formula (A1-1) A11 It is a divalent organic group.

[0068] As X in the above general formula (A1-1) A11 The divalent organic group represented by the following general formula (A1-2) includes a divalent group represented by the following general formula (A1-3), a divalent group represented by the following general formula (A1-4), a divalent group represented by the following general formula (A1-5), a divalent group represented by the following general formula (A1-6), etc.

[0069] [Chemical formula 2]

[0070]

[0071] (Where R A11 It is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A11 is an integer from 0 to 4. * indicates a bonding site. )

[0072] As R in the above general formula (A1-2) A11 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by , for example, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; 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 straight-chain or branched.

[0073] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0074] In the above general formula (A1-2), n A11 It is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of easy availability.

[0075] In n A11 When the integer is 2 or more, multiple R A11 They can be the same or different from each other.

[0076] [Chemical formula 3]

[0077]

[0078] (Where R A12 and R A13 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A12 It is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether 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). A12 and n A13 Each independently represents an integer of 0 to 4. * represents a bonding site. )

[0079] As R in the above general formula (A1-3) A12 and R A13 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by , for example, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; 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. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group and an ethyl group are further preferred.

[0080] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0081] As X in the above general formula (A1-3) A12 The alkylene group having 1 to 5 carbon atoms represented by alkylene group includes, for example, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc. As the alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 3 carbon atoms is preferred, an alkylene group having 1 or 2 carbon atoms is more preferred, and a methylene group is further preferred.

[0082] As X in the above general formula (A1-3) A12 The alkylidene group having 2 to 5 carbon atoms represented by alkylidene group includes, for example, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, etc. Among them, alkylidene group having 2 to 4 carbon atoms is preferred, alkylidene group having 2 or 3 carbon atoms is more preferred, and isopropylidene group is further preferred.

[0083] In the above general formula (A1-3), n A12 and n A13 Each independently represents an integer from 0 to 4.

[0084] In n A12 or A13 When the integer is 2 or more, multiple R A12 Each other or multiple R A13 They may be the same as or different from each other.

[0085] X in the above general formula (A1-3) A12 The divalent group represented by the general formula (A1-3-1) is as follows.

[0086] [Chemical formula 4]

[0087]

[0088] (Where R A14 and R A15Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A13 It is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. A14 and n A15 Each independently represents an integer of 0 to 4. * represents a bonding site. )

[0089] As R in the above general formula (A1-3-1) A14 and R A15 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by , for example, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; 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 straight-chain or branched.

[0090] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0091] As X in the above general formula (A1-3-1) A13 The alkylene group having 1 to 5 carbon atoms represented by alkylene group includes, for example, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc. As the alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 3 carbon atoms is preferred, an alkylene group having 1 or 2 carbon atoms is more preferred, and a methylene group is further preferred.

[0092] As X in the above general formula (A1-3-1) A13 The alkylidene group having 2 to 5 carbon atoms shown in the above formula includes, for example, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, isopentylidene, etc. Among them, alkylidene groups having 2 to 4 carbon atoms are preferred, alkylidene groups having 2 or 3 carbon atoms are more preferred, and isopropylidene is further preferred.

[0093] As X in the above general formula (A1-3-1) A13 Among the above options, an alkylidene group having 2 to 5 carbon atoms is preferred, an alkylidene group having 2 to 4 carbon atoms is more preferred, and an isopropylidene group is further preferred.

[0094] In the above general formula (A1-3-1), n A14 and n A15 Each independently represents an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of easy availability.

[0095] n A14 or A15 When the integer is 2 or more, multiple R A14Each other or multiple R A15 They may be the same as or different from each other.

[0096] As X in the above general formula (A1-3) A12 Among the above options, preferred are alkylene groups having 1 to 5 carbon atoms, alkylidene groups having 2 to 5 carbon atoms, and the divalent group represented by the above general formula (A1-3-1), more preferred are alkylene groups having 1 to 5 carbon atoms, and still more preferred are methylene groups.

[0097] [Chemical formula 5]

[0098]

[0099] (where n A16 is an integer from 0 to 10. * indicates a bonding site. )

[0100] From the viewpoint of easy availability, n in the above general formula (A1-4) is A16 An integer of 0-5 is preferable, an integer of 0-4 is more preferable, and an integer of 0-3 is further preferable.

[0101] [Chemical formula 6]

[0102]

[0103] (where n A17 It is a number from 0 to 5. * indicates a bonding site. )

[0104] [Chemical formula 7]

[0105]

[0106] (Where R A16 and R A17 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. A18 is an integer from 1 to 8. * represents a bonding site. )

[0107] As R in the above general formula (Al-6) A16 and R A17 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by , for example, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; 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 straight-chain or branched.

[0108] In the above general formula (A1-6), n A18 It is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and further preferably 1. A18When the integer is 2 or more, multiple R A16 Each other or multiple R A17 They may be the same as or different from each other.

[0109] Examples of the maleimide resin (A1) include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins.

[0110] Specific examples of the 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-maleimidophenoxy) 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) 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-maleimidophenyl)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfoxide, 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-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidephenoxy)-3,5-dimethyl- α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimide phenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimide phenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimide phenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethane maleimide, biphenyl aralkyl type maleimide, etc. Among them, 2,2-bis[4-(4-maleimide phenoxy)phenyl]propane is preferred. ,

[0111] -Maleimide resin derivative (AY)-

[0112] The maleimide resin derivative (AY) is preferably a resin having a structure derived from the maleimide resin (AX) and a structure derived from a diamine compound [hereinafter, sometimes referred to as "aminomaleimide resin (A2)" or "component (A2)".].

[0113] -Aminomaleimide resin (A2)-

[0114] The aminomaleimide resin (A2) has a structure derived from the maleimide resin (AX) and a structure derived from the diamine compound.

[0115] 《Structure derived from maleimide resin (AX)》

[0116] Examples of the structure derived from the maleimide resin (AX) include a structure 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.

[0117] The structure derived from the maleimide resin (AX) contained in the aminomaleimide resin (A2) may be one kind alone or two or more kinds.

[0118] The content of the structure derived from the maleimide resin (AX) in the 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.

[0119] When the content of the structure derived from the maleimide resin (AX) in the aminomaleimide resin (A2) is within the above range, dielectric properties and handling properties when formed into a resin film tend to be further improved.

[0120] 《Structure derived from diamine compounds》

[0121] Examples of the structure derived from the diamine compound include a structure in which one or both of the two amino groups of the diamine compound and the N-substituted maleimide group of the maleimide resin (AX) undergo Michael addition reaction.

[0122] The structure derived from the diamine compound contained in the aminomaleimide resin (A2) may be a single type or two or more types.

[0123] The amino group contained in the diamine compound is preferably a primary amino group.

[0124] Examples of the structure derived from a diamine compound having two primary amino groups include a group represented by the following general formula (A2-1) and a group represented by the following general formula (A2-2).

[0125] [Chemical formula 8]

[0126]

[0127] (Where X A21 is a divalent organic group, and * indicates a bonding site. )

[0128] X in the above general formula (A2-1) and the above general formula (A2-2) A21 It is a divalent organic group, and corresponds to a divalent group obtained by removing two primary amino groups from a diamine compound.

[0129] X in the above general formula (A2-1) and the above general formula (A2-2) A21 Preferred is a divalent group represented by the following general formula (A2-3).

[0130] [Chemical formula 9]

[0131]

[0132] (Where R A21 and R A22 Each independently represents 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 It is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether 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 the following general formula (A2-3-2).A21 and n A22 Each independently represents an integer of 0 to 4. * represents a bonding site. )

[0133] [Chemical formula 10]

[0134]

[0135] (Where R A23 and R A24 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A23 An alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, a m-phenylene diisopropylidene group, a p-phenylene diisopropylidene group, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. A23 and n A24 Each independently represents an integer of 0 to 4. * represents a bonding site. )

[0136] [Chemical formula 11]

[0137]

[0138] (Where R A25 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A24 and X A25 Each is independently an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. A25 is an integer from 0 to 4. * indicates a bonding site. )

[0139] As the above general formula (A2-3), R in the above general formula (A2-3-1) and the above general formula (A2-3-2) A21 , R A22 , R A23 , R A24 and R A25 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by , for example, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; 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. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group and an ethyl group are further preferred.

[0140] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0141] As X in the above general formula (A2-3) A22, X in the above general formula (A2-3-1) A23 And X in the above general formula (A2-3-2) A24 and X A25 The alkylene group having 1 to 5 carbon atoms represented by alkylene group includes, for example, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc. As the alkylene group having 1 to 5 carbon atoms, an alkylene group having 1 to 3 carbon atoms is preferred, an alkylene group having 1 or 2 carbon atoms is more preferred, and a methylene group is further preferred.

[0142] As X in the above general formula (A2-3) A22 , X in the above general formula (A2-3-1) A23 And X in the above general formula (A2-3-2) A24 and X A25 The alkylidene group having 2 to 5 carbon atoms shown in the above formula (I) includes, for example, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, isopentylidene, etc. As the alkylidene group having 2 to 5 carbon atoms, an alkylidene group having 2 to 4 carbon atoms is preferred, an alkylidene group having 2 or 3 carbon atoms is more preferred, and isopropylidene is further preferred.

[0143] In the above general formula (A2-3), n A21 and n A22 Each independently represents an integer of 0 to 4, and is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 2, from the viewpoint of easy availability.

[0144] n A21 or A22 When the integer is 2 or more, multiple R A21 Each other or multiple R A22 They may be the same as or different from each other.

[0145] In the above general formula (A2-3-1), n A23 and n A24 Each independently represents an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of easy availability.

[0146] n A23 or A24 When the integer is 2 or more, multiple R A23 Each other or multiple R A24 They may be the same as or different from each other.

[0147] In the above general formula (A2-3-2), n A25 It is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of easy availability.

[0148] n A25 When the integer is 2 or more, multiple R A25 They may be the same as or different from each other.

[0149] In addition, X in the above general formula (A2-1) and the above general formula (A2-2) A21 It may be a divalent group having a structure represented by the following general formula (A2-4), or it may be a divalent group represented by the following general formula (A2-5).

[0150] [Chemical formula 12]

[0151]

[0152] (Where R A26 and R A27 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group. * represents a bonding site. )

[0153] [Chemical formula 13]

[0154]

[0155] (Where R A26 and R A27 The same as the group in the above general formula (A2-4), R A28 and R A29 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group. A26 and X A27 Each is independently a divalent organic group, n A26 is an integer from 2 to 100. * indicates a bonding site. )

[0156] As R in the above general formulas (A2-4) and (A2-5) A26 ~R A29 The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the formula (a) may include, for example, an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group; an alkenyl group having 2 to 5 carbon atoms; an alkynyl group having 2 to 5 carbon atoms, and the like. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is further preferred.

[0157] As R A26 ~R A29 The substituent of the phenyl group in the substituted phenyl group represented by ' may be the above-mentioned aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0158] As X A26 and X A27 Examples of the divalent organic group represented by include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, and a divalent linking group composed of a combination of these groups.

[0159] Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, and a propylene group.

[0160] Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms.

[0161] Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms.

[0162] Examples of the arylene group include arylene groups having 6 to 20 carbon atoms, such as a phenylene group and a naphthylene group.

[0163] Among them, as X A26 and X A27 , preferably an alkylene group and an arylene group, and more preferably an alkylene group.

[0164] n A26 is an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, and further preferably an integer of 5 to 30. A26 When the integer is 2 or more, multiple R A26 Each other or multiple R A27 They may be the same as or different from each other.

[0165] The content of the structure derived from the diamine compound 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 further preferably 10 to 40% by mass.

[0166] When the content of the structure derived from the diamine compound in the aminomaleimide resin (A2) is within the above range, dielectric properties, heat resistance, flame retardancy and glass transition temperature tend to be further improved.

[0167] Examples of the diamine compound 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, 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( 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- Aromatic diamine compounds such as bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone and 9,9-bis(4-aminophenyl)fluorene; and organosilicon compounds having two primary amino groups.

[0168] In addition, in this specification, an "aromatic diamine compound" means a compound which has two amino groups directly bonded to an aromatic ring.

[0169] Among them, from the viewpoint of excellent solubility in organic solvents, reactivity, heat resistance, dielectric properties and low water absorption, the diamine compound is preferably 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, and 3,3'-diethyl-4,4'-diaminodiphenylmethane is more preferred. In addition, from the viewpoint of low thermal expansion, an organosilicon compound having two primary amino groups is preferred.

[0170] As the organosilicon compound having two primary amino groups, an organosilicon compound having primary amino groups at both terminals is preferred.

[0171] The primary amino group equivalent of the organosilicon 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 further preferably 500 to 1,000 g / mol.

[0172] The equivalent ratio (Ta2 / Tal) ​​of the total equivalent weight (Ta2) of the groups derived from the -NH2 group of the diamine compound in the aminomaleimide resin (A2) to the total equivalent weight (Tal) of the groups derived from the N-substituted maleimide group of the maleimide resin (AX) is not particularly limited, but is preferably 0.05 to 10, more preferably 1 to 8, and further preferably 3 to 7 from the viewpoint of dielectric properties, heat resistance, flame retardancy, and glass transition temperature. It should be noted that the above-mentioned groups derived from the -NH2 group of the diamine compound also include -NH2 itself. In addition, the above-mentioned groups derived from the N-substituted maleimide group of the maleimide resin (AX) also include the N-substituted maleimide group itself.

[0173] The weight average molecular weight (Mw) of the aminomaleimide resin (A2) is not particularly limited, but is preferably 400 to 10,000, more preferably 1,000 to 5,000, further preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000 from the viewpoint of handling properties and moldability.

[0174] The aminomaleimide resin (A2) can be produced by, for example, reacting the maleimide resin (AX) with a diamine compound in an organic solvent.

[0175] By reacting the maleimide resin (AX) and the diamine compound, an aminomaleimide resin (A2) in which the maleimide resin (AX) and the diamine compound are subjected to a Michael addition reaction can be obtained.

[0176] When the maleimide resin (AX) and the diamine compound are reacted, a reaction catalyst may be used as necessary.

[0177] The reaction temperature of 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 gelation of the product during the reaction.

[0178] From the viewpoint of productivity and sufficient progress of the reaction, the reaction time of 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.

[0179] However, these reaction conditions can be appropriately adjusted according to the types of raw materials used, and are not particularly limited.

[0180] (Epoxy resin)

[0181] As the epoxy resin, an epoxy resin having two or more epoxy groups is preferred.

[0182] Epoxy resins are classified into, for example, glycidyl ether epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, etc. Among them, glycidyl ether epoxy resins are preferred.

[0183] Epoxy resins are classified into various types according to the difference in the main skeleton.

[0184] Specifically, epoxy resins are classified into bisphenol-type epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; phenolic epoxy resins such as bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, and naphthol novolac epoxy resin; aralkyl epoxy resins such as phenol aralkyl epoxy resin, biphenyl aralkyl epoxy resin, and naphthol aralkyl epoxy resin; stilbene epoxy resin; naphthylene ether epoxy resin; biphenyl epoxy resin; dihydroanthracene epoxy resin; epoxy resin containing a saturated dicyclopentadiene skeleton; cyclohexanedimethanol epoxy resin; spiro ring-containing epoxy resin; heterocyclic epoxy resin; alicyclic epoxy resin; aliphatic chain epoxy resin; rubber-modified epoxy resin, etc. Among them, epoxy resins containing a biphenyl structure are preferred, and biphenyl aralkyl type epoxy resins are more preferred.

[0185] The resin composition of the present embodiment preferably contains, as (A) the thermosetting resin, one or more selected from maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins, and more preferably contains an epoxy resin.

[0186] The content of one or more selected from maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins in the thermosetting resin (A) 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.

[0187] The content of the epoxy resin in the (A) 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.

[0188] In the resin composition of the present embodiment, the content of the (A) thermosetting resin is not particularly limited, and is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, and further preferably 80 to 100 mass %, relative to the total amount (100 mass %) of the resin components in the resin composition of the present embodiment.

[0189] When the content of the (A) thermosetting resin is within the above range, heat resistance, formability, processability, and copper foil adhesion tend to be more favorable.

[0190] Here, in this specification, "resin component" refers to a resin and a compound that forms a resin by a curing reaction. However, (D) a curing accelerator is not included in the resin component.

[0191] The content of the resin component in the resin composition of the present embodiment is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 50% by mass, relative to the total solid content (100% by mass) of the resin composition of the present embodiment.

[0192] If the content of the resin component is above the above lower limit, there is a tendency that heat resistance, formability, processability and copper foil adhesion are easily improved. In addition, if the content of the resin component is below the above upper limit, there is a tendency that low thermal expansion is easily improved.

[0193] <(B) Spherical zinc molybdate>

[0194] The prepreg of the present embodiment has excellent drill processability and copper foil adhesion by making the resin composition contain (B) spherical zinc molybdate. The reason why the prepreg of the present embodiment has excellent copper foil adhesion is still uncertain, but one of the reasons is speculated to be 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.

[0195] It should be noted that the zinc molybdate in this embodiment is a salt of molybdic acid and zinc, and its composition formula is represented by, for example, ZnXMoYO4(0.5<X<2.5, 0.5<Y<2.5), ZnXMoYO4(OH)Z(0.5<X<2.5, 0.5<Y<2.5, 0.5<Z<2.5), etc.

[0196] In the present embodiment, the term "spherical" means that the circularity calculated by the following formula using the area and the perimeter measured from the photograph of the target particle is 90 or more.

[0197] Roundness = {4π×(area)÷(circumference) 2}×100

[0198] The closer the circularity is to 100, the closer it is to a true sphere. From the viewpoint of copper foil adhesion, the circularity of the spherical zinc molybdate (B) in this embodiment is preferably 90 to 100, more preferably 93 to 100, and even more preferably 95 to 100.

[0199] A more specific method for measuring the circularity is described in the Examples.

[0200] (B) Average particle size of spherical zinc molybdate (D 50 ) is not particularly limited, but from the viewpoint of copper foil adhesion, it is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 5 μm, and particularly preferably 0.5 to 1.5 μm.

[0201] It should be noted that, in this specification, the average particle size (D 50 ) refers to the particle size corresponding to the point where the volume is 50% when the total volume of the particles is set as 100% and the cumulative frequency distribution curve based on the particle size is obtained. Average particle size (D 50 ) For example, it can be measured using a particle size distribution measuring device using a laser diffraction scattering method.

[0202] In the resin composition of the present embodiment, the content of the spherical zinc molybdate (B) is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, and further preferably 0.5 to 5% by mass, relative to the total solid content (100% by mass) of the resin composition.

[0203] When the content of the spherical zinc molybdate (B) is within the above range, drill processability and copper foil adhesion tend to be more favorable.

[0204] <(C) Inorganic fillers>

[0205] The resin composition of the present embodiment preferably further contains (C) an inorganic filler.

[0206] The resin composition of the present embodiment tends to easily obtain more excellent low thermal expansion property and heat resistance by containing the (C) inorganic filler.

[0207] It should be noted that, in the present embodiment, the concept of the (C) inorganic filler does not include the (B) spherical zinc molybdate.

[0208] (C) The inorganic filler may be used alone or in combination of two or more.

[0209] (C) Inorganic fillers include, for example, silica, alumina, titanium oxide, mica, beryllium oxide, 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 them, from the viewpoint 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 further preferred.

[0210] As silica, for example, precipitated silica with high water content produced by a wet method, and dry-process silica produced by a dry method and containing almost no bound water, etc., can be cited. As dry-process silica, for example, crushed silica, fumed silica, fused silica, etc. can be cited, depending on the production method. Among them, fused silica is preferred from the viewpoint of dispersibility and formability.

[0211] (C) Average particle size of inorganic filler (D 50 ) is not particularly limited, but from the viewpoint of the dispersibility and fine wiring properties of the (C) inorganic filler, it is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 5 μm, and particularly preferably 0.3 to 2 μm.

[0212] Examples of the shape of the (C) inorganic filler include spherical shapes and crushed shapes, and a spherical shape is preferred.

[0213] In the resin composition of the present embodiment, a coupling agent may be used for the purpose of improving the dispersibility of the (C) inorganic filler and the adhesion between the (C) inorganic filler and the organic component. As the coupling agent, for example, a silane coupling agent, a titanate coupling agent, etc. may be mentioned. Among them, a silane coupling agent is preferred.

[0214] When the resin composition of the present embodiment contains (C) an inorganic filler, the content of the (C) inorganic filler is not particularly limited, and is preferably 10 to 80% by mass, more preferably 30 to 75% by mass, further preferably 40 to 70% by mass, further preferably 50 to 67% by mass, and particularly preferably 55 to 65% by mass, relative to the total solid content (100% by mass) of the resin composition.

[0215] If the content of the inorganic filler (C) is above the lower limit, low thermal expansion and heat resistance tend to be better. In addition, if the content of the inorganic filler (C) is below the upper limit, formability and copper foil adhesion tend to be better.

[0216] <(D) Curing Accelerator>

[0217] The resin composition of the present embodiment preferably further contains (D) a curing accelerator.

[0218] The resin composition of the present embodiment contains the (D) curing accelerator, whereby the curability is improved and there is a tendency that more excellent copper foil adhesion is easily obtained.

[0219] (D) The curing accelerator may be used alone or in combination of two or more.

[0220] (D) The curing accelerator includes, for example, 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-masked imidazole compounds such as an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; organic peroxides such as diisopropyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylperoxyisopropyl monocarbonate, and α,α'-bis(tert-butylperoxy)diisopropylbenzene; carboxylates of manganese, cobalt, zinc, and the like;

[0221] Among them, isocyanate-masked imidazole compounds are preferred from the viewpoint of the curing acceleration effect and storage stability.

[0222] When the resin composition of the present embodiment contains (D) a curing accelerator, the content of the (D) 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, relative to 100 parts by mass of the (A) thermosetting resin.

[0223] When the content of the curing accelerator (D) is at least the above lower limit, a sufficient curing acceleration effect tends to be easily obtained. On the other hand, when the content of the curing accelerator (D) is at most the above upper limit, storage stability tends to be more favorable.

[0224] <Other optional ingredients>

[0225] The resin composition of the present embodiment may further contain one or more other arbitrary components selected from resin materials other than the above-mentioned components, flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, organic solvents and additives other than these, as needed.

[0226] The above-mentioned optional components may be used alone or in combination of two or more.

[0227] The content of the above-mentioned optional components in the resin composition of the present embodiment is not particularly limited, and may be used as needed within a range that does not inhibit the effects of the present embodiment.

[0228] In addition, the resin composition of the present embodiment may not contain the above-mentioned arbitrary components depending on the desired performance.

[0229] (Organic Solvent)

[0230] The resin composition of the present embodiment may contain an organic solvent from the viewpoint of easy handling and easy production of a prepreg.

[0231] The organic solvent may be used alone or in combination of two or more.

[0232] In addition, in this specification, the resin composition containing an organic solvent may be referred to as a resin varnish.

[0233] Examples of the organic solvent include alcohol 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 atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide; ester solvents such as γ-butyrolactone, and the like.

[0234] Among them, alcohol solvents, ketone solvents, nitrogen atom-containing solvents, and aromatic hydrocarbon solvents are preferred from the viewpoint of solubility, aromatic hydrocarbon solvents are more preferred, and toluene is further preferred.

[0235] <Method for producing resin composition>

[0236] The resin composition of the present embodiment can be manufactured by mixing the components. At this time, the components can be dissolved or dispersed while stirring. The mixing order, temperature, time and other conditions are not particularly limited and can be arbitrarily set according to the types of raw materials.

[0237] 〔Fiber base material〕

[0238] The fiber base material contained in the prepreg of this embodiment has a unit weight of 50 g / m 2 above.

[0239] By making the basis weight of the fiber base material 50 g / m 2 As described above, the prepreg of the present embodiment has excellent mechanical strength.

[0240] From the viewpoint of mechanical strength of the prepreg, the weight per unit area of ​​the fiber substrate is preferably 60 g / m 2 More preferably 70g / m 2 More preferably, 80 g / m 2 In addition, from the perspective of high-density wiring, 150 g / m 2 Below, more preferably 140g / m 2 Below, more preferably 130g / m 2 Below, particularly preferably 120g / m 2 the following.

[0241] From the viewpoint of mechanical strength of the prepreg and high-density wiring, the basis weight of the fiber substrate is preferably 50 to 150 g / m 2 , more preferably 60 to 140 g / m 2 , more preferably 70 to 130 g / m 2 , particularly preferably 80 to 120 g / m 2 .

[0242] From the viewpoint of mechanical strength of the prepreg, the thickness of the fiber substrate is preferably 50 μm or more, more preferably 60 μm or more, further preferably 70 μm or more, and particularly preferably 80 μm or more. From the viewpoint of high-density wiring, it is preferably 150 μm or less, more preferably 140 μm or less, further preferably 130 μm or less, and particularly preferably 120 μm or less.

[0243] The thickness of the fiber substrate is not particularly limited, but is preferably 50 to 150 μm, more preferably 60 to 140 μm, further preferably 70 to 130 μm, and particularly preferably 80 to 120 μm from the viewpoint of mechanical strength of the prepreg and high-density wiring.

[0244] The fiber base material has a shape of, for example, woven fabric, nonwoven fabric, roving, chopped strand mat, surface mat, or the like.

[0245] From the viewpoint of the impregnation property of the resin composition, etc., the fiber base material may be a fiber base material surface-treated with a coupling agent, or may be a fiber base material subjected to a mechanical fiber-opening treatment.

[0246] As the fibers constituting the fiber substrate, there can be cited inorganic fibers such as glass fibers; organic fibers such as polyimide, polyester, tetrafluoroethylene, etc.; mixtures thereof, etc. Among them, inorganic fibers are preferred, and glass fibers are more preferred from the viewpoint of low thermal expansion. From the same viewpoint, the fiber substrate is preferably glass cloth.

[0247] Examples of the glass fiber include E glass, D glass, T glass, and S glass. Among them, from the viewpoint of low thermal expansion, at least one selected from D glass, T glass, and S glass is preferred.

[0248] In addition, the representative compositions of E glass, D glass, T glass, and S glass are as follows.

[0249] 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%)

[0250] 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%),

[0251] T glass: SiO2 (64-66 mass%), Al2O3 (24-26 mass%), MgO (9-11 mass%)

[0252] S glass: SiO2 (62-65 mass%), Al2O3 (20-25 mass%), CaO (0-0.01 mass%), MgO (10-15 mass%), B2O3 (0-0.01 mass%), Na2O and K2O (0-1 mass%)

[0253] The content of SiO2 in the glass fiber is not particularly limited, but is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, further preferably 50 to 80% by mass, and particularly preferably 60 to 75% by mass.

[0254] If the SiO2 in the glass fiber has a content of more than the above lower limit, there is a trend that the low thermal expansion and low warpage of the prepreg are excellent. In addition, if the SiO2 in the glass fiber has a content of less than the above upper limit, there is a trend that the drill processability of the prepreg is easy to become better.

[0255] [Method for producing prepreg]

[0256] The prepreg of the present embodiment can be produced, for example, by impregnating a fiber base material with a resin composition and then subjecting the resin composition to a B-stage.

[0257] As a method for impregnating the fiber base material with the resin composition, for example, a hot melt method, a solvent method, or the like can be used.

[0258] The hot melt method is a method of impregnating a fiber base material with a resin composition that does not contain an organic solvent.

[0259] One form of the hot melt method is a method in which the resin composition of the present embodiment that does not contain an organic solvent is temporarily applied to a coated paper having good releasability, and then the applied resin composition is laminated on a fiber base material for impregnation.

[0260] As another aspect of the hot melt method, there is a method in which the resin composition of the present embodiment that does not contain an organic solvent is directly applied to a fiber base material using a die coater or the like to perform impregnation.

[0261] The solvent method is a method of impregnating a fiber substrate with a resin composition containing an organic solvent. Specifically, for example, a method of impregnating a fiber substrate with the resin composition of the present embodiment containing an organic solvent, drying to remove the organic solvent, and B-stage the resin composition can be cited.

[0262] The drying temperature is not particularly limited, but is preferably 50 to 200°C, more preferably 100 to 190°C, and even more preferably 150 to 180°C from the viewpoint of productivity and moderately B-staging the resin composition.

[0263] The drying time is not particularly limited, but is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and even more preferably 3 to 10 minutes from the viewpoint of productivity and proper B-stage of the resin composition.

[0264] The content of the resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 30 to 80% by mass, more preferably 35 to 70% by mass, and even more preferably 40 to 60% by mass from the viewpoint of moldability.

[0265] [Laminated board]

[0266] The laminated plate of the present embodiment is a laminated plate including a cured product of the prepreg of the present embodiment and a metal foil.

[0267] In addition, the laminated plate having a metal foil is sometimes also referred to as a metal-clad laminated plate.

[0268] The metal of the metal foil is not particularly limited, and examples thereof include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements.

[0269] The laminated plate of the present embodiment can be produced, for example, by placing a metal foil on one or both surfaces of the prepreg of the present embodiment and then performing heat-pressing molding.

[0270] Usually, the laminated plate of the present embodiment is obtained by curing the B-staged prepreg through the heat and pressure molding.

[0271] In the case of heat and pressure molding, only one prepreg may be used, or two or more prepregs may be stacked and used.

[0272] For the heat and pressure molding, for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used.

[0273] The conditions for the heat-press molding are not particularly limited, and for example, the conditions may be a temperature of 100 to 300° C., a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.

[0274] [Printed wiring board]

[0275] The printed wiring board of the present embodiment is a printed wiring board having a cured product of the prepreg of the present embodiment.

[0276] The printed wiring board of the present embodiment can be manufactured, for example, by forming a conductor circuit on the cured product of the prepreg of the present embodiment using a known method. In addition, a multilayer printed wiring board can also be manufactured by further performing a multilayer bonding process as required. The conductor circuit can be formed, for example, by appropriately performing a hole opening process, a metal plating process, an etching of a metal foil, etc.

[0277] [Semiconductor package]

[0278] The semiconductor package of the present embodiment includes the printed wiring board of the present embodiment and a semiconductor element.

[0279] The semiconductor package of the present embodiment can be manufactured by, for example, mounting a semiconductor chip, a memory, and the like on a printed wiring board of the present embodiment by a known method.

[0280] Example

[0281] Hereinafter, the present embodiment will be described in detail with reference to examples, but the present embodiment is not limited to the following examples.

[0282] In addition, in each example, the weight average molecular weight (Mw) was measured by the following method.

[0283] The conversion was performed by gel permeation chromatography (GPC) based on a calibration curve using standard polystyrene. The calibration curve used standard polystyrene: TSK standard POLYSTYRENE (models; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name], and was approximated by a cubic equation. The measurement conditions of GPC are shown below.

[0284] Device:

[0285] Pump: -L-6200 model [manufactured by Hitachi High-Technologies Co., Ltd.]

[0286] Detector - L-3300 RI [manufactured by Hitachi High-Technologies Co., Ltd.]

[0287] Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Co., Ltd.]

[0288] Column: Guard column; TSK Guardcolumn HHR-L+ column; TSKgel G4000HHR-+TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade names)

[0289] Column size: 6.0×40mm (guard column), 7.8×300mm (column)

[0290] Eluent: Tetrahydrofuran

[0291] Sample concentration: 30mg / 5mL

[0292] Injection volume: 20 μL

[0293] Flow rate: 1.00mL / min

[0294] Measurement temperature: 40℃

[0295] Preparation Example 1: Preparation of aminomaleimide resin

[0296] In a 5-liter reaction vessel with a thermometer, a stirring device, and a moisture meter with a reflux condenser, 100 parts by mass of 2,2-bis[4-(4-maleimide phenoxy) phenyl] propane, 5.6 parts by mass of an organosilicon 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 the mixture was reacted for 2 hours while refluxing. The mixture was concentrated at reflux temperature for 3 hours to produce a solution of aminomaleimide resin having a solid content concentration of 65% by mass. The weight average molecular weight (Mw) of the obtained aminomaleimide resin was about 2,700.

[0297] [Method for measuring roundness]

[0298] Zinc molybdate was observed at 5,000 times using a scanning electron microscope (SEM) (manufactured by JEOL Ltd., product name "JSM-6010PLUS / LA"). In the obtained SEM photograph, the area and perimeter of 10 random particles were measured. Next, the circularity of each particle was calculated based on the following formula using the obtained area and perimeter, and the value obtained by averaging these was used as the circularity of zinc molybdate used in each example.

[0299] Roundness = {4π×(area)÷(circumference) 2}×100

[0300] Examples 1-2, Comparative Examples 1-2

[0301] (Manufacture of resin composition)

[0302] The components listed in Table 1 were stirred and mixed with methyl ethyl ketone to prepare a varnish-like resin composition having a solid content concentration of 60% by mass. In Table 1, the unit of the amount of each component is part by mass, and in the case of a solution, it refers to part by mass converted to solid content.

[0303] (Manufacturing of prepreg)

[0304] The varnish-like resin composition obtained above was impregnated into a glass cloth (weight per unit area: 114 g / m 2 , glass type: T glass, glass cloth thickness: 98 μm), and heated and dried at 120° C. for 3 minutes to obtain a prepreg. The content of the resin composition in the prepreg was 50% by mass.

[0305] (Manufacture of copper-clad laminates)

[0306] Seven sheets of the prepreg obtained above were stacked, and copper foils with a thickness of 12 μm (Mitsui Metals Co., Ltd., trade name "3EC-M3-VLP-12", Rz of the M surface (rough surface): 3.0 μm) were arranged on the upper and lower sides so that the M surface (rough surface) was in contact with the prepreg. The laminate was heated and pressed at a temperature of 240°C and a pressure of 3.0 MPa for 90 minutes to obtain a copper-clad laminate.

[0307] [Evaluation method]

[0308] Each evaluation was performed according to the following method. The results are shown in Table 1.

[0309] (Method for measuring drilling position offset)

[0310] Three copper-clad laminates were overlapped, and an aluminum foil with a thickness of 0.15 mm was placed on top, and a paper phenolic board with a thickness of 1.5 mm was placed below. Next, 10,000 holes were drilled using a φ0.15 mm drill (manufactured by Via Mechanics Co., Ltd., trade name "ND-1V212") at a rotation speed of 200 krpm, a feed speed of 2 m / min, and a chip load of 10 μm / rev. The positional offset of the hole on the lower side (drill outlet side) of the third sheet of the three overlapping copper-clad laminates was measured using a hole position accuracy measuring machine (manufactured by Via Mechanics Co., Ltd., trade name "HT-1AM"), and the average +3σ (σ: standard deviation) of the positional offset of 10,000 holes was calculated as an indicator of drilling position accuracy.

[0311] (Method for measuring the peel strength of copper foil)

[0312] The copper foil of the copper-clad laminate produced above was processed into a 5 mm wide straight line by etching, and used as a test piece. The formed straight copper foil was installed in a small table tester (manufactured by Shimadzu Corporation, trade name "EZ-TEST"), and peeled in a 90° direction at room temperature (25°C) to measure the copper foil peel strength. It should be noted that the tensile speed when peeling the copper foil was set to 50 mm / min.

[0313] [Table 1]

[0314] Table 1

[0315]

[0316] It should be noted that the details of the components shown in Table 1 are as follows.

[0317] [(A) ingredient]

[0318] Thermosetting resin 1: aminomaleimide resin prepared in Preparation Example 1

[0319] Thermosetting resin 2: Biphenyl aralkyl type epoxy resin, "NC-3000" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275 g / eq

[0320] [(B) ingredient]

[0321] Spherical zinc molybdate: average particle size (D 50 )0.9μm, roundness 99

[0322] [Comparison of ingredients]

[0323] Talc loaded with zinc molybdate: flaky, with a roundness of less than 90, and a loading amount of zinc molybdate of 20% by mass

[0324] [(C) ingredient]

[0325] ·Fused silica: Average particle size (D 50 )0.5μm, spherical fused silica

[0326] [(D) ingredient]

[0327] Curing accelerator: Isocyanate-masked imidazole, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "G-8009L"

[0328] According to Table 1, the prepregs of Examples 1 and 2 of the present embodiment can reduce the amount of drilling position deviation while maintaining the copper foil peel strength, compared with the prepreg of Comparative Example 1 to which (B) spherical zinc molybdate is not added. On the other hand, the prepreg of Comparative Example 2 to which talc loaded with zinc molybdate other than (B) spherical zinc molybdate is added can reduce the amount of drilling position deviation, but the copper foil peel strength is greatly reduced.

Claims

1. A prepreg comprising a resin composition and a fiber substrate, wherein the resin composition comprises (A) a thermosetting resin and (B) spherical zinc molybdate, The fiber substrate has a unit area weight of 50 g / m 2 above.

2. The prepreg according to claim 1, wherein The fiber substrate has a thickness of 50 μm or more.

3. The prepreg according to claim 1 or 2, wherein: The fiber substrate is glass cloth.

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

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

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

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

8. The prepreg according to claim 7, wherein The (A) thermosetting resin further contains an epoxy resin. 9 . A laminate comprising a cured product of the prepreg according to claim 1 or 2 and a metal foil. 10 . A printed wiring board comprising a cured product of the prepreg according to claim 1 or 2 . 11 . A semiconductor package comprising the printed wiring board according to claim 10 and a semiconductor element.

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