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

Abstract

The invention provides a resin composition, a prepreg using the resin composition, a laminated plate, a resin film, a printed wiring board and a semiconductor package. The resin composition contains: (A) a resin including a structure derived from a maleimide resin (a) having one or more N-substituted maleimide groups and a structure derived from an amine compound (b) having one or more amino groups; and (B) a maleimide resin having three or more N-substituted maleimide groups.

Description

Technical Field

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

[0002] With the recent trend of miniaturization and higher performance of electronic devices, the wiring density and integration of printed wiring boards are increasing. In conjunction with this, printed wiring boards are required to have higher reliability than conventional printed wiring boards.

[0003] As a property required of the insulating layer of a printed wiring board, good heat resistance can be cited. In particular, in recent years, due to the increased awareness of environmental issues, the semiconductor chip mounting process that does not use lead-free solder has become the mainstream, and the insulating layer is required to have heat resistance that can be used for mounting at a higher reflow temperature.

[0004] The insulating layer of the printed wiring board uses thermosetting resins such as maleimide resins and epoxy resins. Compared with cured products using epoxy resins, cured products using maleimide resins have the advantage of being easy to obtain excellent heat resistance, but maleimide resins have problems such as requiring high curing temperatures, low solvent solubility, and difficult handling.

[0005] Patent Document 1 discloses a thermosetting resin composition comprising a resin composition having an unsaturated maleimide group obtained by reacting a maleimide compound (a) having at least two N-substituted maleimide groups in one molecule with an amine compound (b) having at least two primary amino groups in one molecule.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2013-064136 Summary of the invention

[0009] Problems to be solved by the invention

[0010] According to the technology of Patent Document 1, a thermosetting resin composition can be obtained which has good resin curing properties, i.e., does not require high-temperature and long-term treatment when laminating prepregs, and has good curing properties and storage stability of varnish and prepregs, and is excellent in chemical resistance, heat resistance and adhesion.

[0011] However, in the manufacturing process of printed wiring boards, desmear treatment is performed for the purpose of removing residual components after hole opening processing of the insulating layer. If the insulating layer is excessively dissolved by the desmear treatment, the aperture of the through hole or the like may change from a predetermined size, or the adhesion to the conductor layer may be reduced. Therefore, the insulating layer is required to have desmear resistance to suppress excessive dissolution during the desmear treatment.

[0012] In recent years, the wiring density in the field of printed wiring boards has increased significantly, and higher desmear resistance than ever before has been required. According to the research of the present inventors, the technology disclosed in Patent Document 1 has room for improvement in desmear resistance.

[0013] In view of such a current situation, an object of the present embodiment is to provide a resin composition having excellent desmear resistance, and a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package using the resin composition.

[0014] Means for solving problems

[0015] 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.

[0016] That is, this embodiment relates to the following [1] to

[12] .

[0017] [1] A resin composition comprising: (A) a resin comprising a structure derived from a maleimide resin (a) having one or more N-substituted maleimide groups and a structure derived from an amine compound (b) having one or more amino groups, and

[0018] (B) A maleimide resin having three or more N-substituted maleimide groups.

[0019] [2] The resin composition according to [1] above, wherein the amine compound (b) having one or more amino groups is a siloxane compound having one or more amino groups.

[0020] [3] The resin composition according to [1] or [2], wherein the component (B) is a maleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring.

[0021] [4] The resin composition according to the above [3], wherein the maleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring is a maleimide resin represented by the following general formula (B-1).

[0022] [Chemical formula 1]

[0023]

[0024] (Where X B1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, n B1 is an integer from 2 to 5.)

[0025] [5] The resin composition according to [4], wherein X in the general formula (B-1) is B1 It is an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.

[0026] [6] The resin composition according to any one of [1] to [5], wherein the ratio of the content of the component (B) to the content of the component (A) [component (B) / component (A)] is 0.4 to 10 on a mass basis.

[0027] [7] The resin composition according to any one of [1] to [6], further comprising (C) an epoxy resin.

[0028] [8] A prepreg comprising the resin composition according to any one of [1] to [7] above or a semi-cured product of the resin composition.

[0029] [9] A laminate comprising a cured product of the resin composition according to any one of [1] to [7] above and a metal foil.

[0030]

[10] A resin film comprising the resin composition according to any one of [1] to [7] above or a semi-cured product of the resin composition.

[0031]

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

[0032]

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

[11] above and a semiconductor element.

[0033] Effects of the Invention

[0034] According to the present embodiment, a resin composition having excellent desmear resistance, and a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package using the resin composition can be provided. DETAILED DESCRIPTION

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] Unless otherwise specified, each component and material exemplified in the present specification may be used alone or in combination of two or more.

[0040] 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.

[0041] In this specification, "solid content" refers to components other than solvents, and also includes substances that are liquid, syrupy, and waxy at room temperature. Here, in this specification, room temperature refers to 25°C.

[0042] The number average molecular weight (Mn) 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.

[0043] The "semi-cured product" in this specification has the same meaning as the resin composition in the B-stage state in JIS K 6800 (1985), and the "cured product" has the same meaning as the resin composition in the C-stage state in JIS K 6800 (1985).

[0044] 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.

[0045] A mode in which the matters described in this specification are arbitrarily combined is also included in this embodiment.

[0046] [Resin composition]

[0047] The resin composition of this embodiment is a resin composition containing:

[0048] (A) a resin comprising a structure derived from a maleimide resin (a) having one or more N-substituted maleimide groups and a structure derived from an amine compound (b) having one or more amino groups [hereinafter, sometimes referred to as "(A) modified maleimide resin"], and

[0049] (B) A maleimide resin having three or more N-substituted maleimide groups [hereinafter, sometimes referred to as "(B) polymaleimide resin"].

[0050] In addition, in this specification, each component may be abbreviated as (A) component, (B) component, etc., respectively, and the same abbreviation method may be used for other components.

[0051] Hereinafter, each component which can be contained in the resin composition of this embodiment is demonstrated sequentially.

[0052] <(A) Modified maleimide resin>

[0053] The modified maleimide resin (A) is not particularly limited as long as it is a resin including a structure derived from a maleimide resin (a) having one or more N-substituted maleimide groups and a structure derived from an amine compound (b) having one or more amino groups.

[0054] (A) The modified maleimide resin may be used alone or in combination of two or more.

[0055] It should be noted that, in the following description, the maleimide resin (a) having one or more N-substituted maleimide groups is sometimes referred to as "maleimide resin (a1)". In addition, in the following description, the amine compound (b) having one or more amino groups is sometimes referred to as "amine compound (a2)".

[0056] (Structure derived from maleimide resin (a1))

[0057] The structure derived from the maleimide resin (a1) is preferably a structure formed by Michael addition reaction of at least one N-substituted maleimide group of the maleimide resin (a1) and an amino group of the amine compound (a2).

[0058] The structure derived from the maleimide resin (a1) contained in the (A) modified maleimide resin may be one kind alone or two or more kinds.

[0059] The content of the structure derived from the maleimide resin (a1) in the modified maleimide resin (A) is not particularly limited, but is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, and even more preferably 40 to 70% by mass.

[0060] When the content of the structure derived from the maleimide resin (a1) in the (A) modified maleimide resin is within the above range, heat resistance, dielectric properties, and handling properties when formed into a resin film tend to be further improved.

[0061] [Maleimide resin (a1)]

[0062] The maleimide resin (a1) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups.

[0063] From the viewpoint of conductor adhesion and heat resistance, the maleimide resin (a1) is preferably a bismaleimide resin having two N-substituted maleimide groups or a polymaleimide resin having three or more N-substituted maleimide groups, and more preferably an aromatic bismaleimide resin having two N-substituted maleimide groups bonded to an aromatic ring or an aromatic polymaleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring.

[0064] As a bismaleimide resin which is preferably the maleimide resin (a1), a maleimide resin represented by the following general formula (a1-1) can be mentioned.

[0065] [Chemical formula 2]

[0066]

[0067] (Where X a11 is a divalent organic group.)

[0068] X in the above general formula (a1-1) a11 It is a divalent organic group.

[0069] As X in the above general formula (a1-1) a11 Examples of the divalent organic group include a divalent group represented by the following general formula (a1-2), a divalent group represented by the following general formula (a1-3), and a divalent group represented by the following general formula (a1-4).

[0070] [Chemical formula 3]

[0071]

[0072] (Where R a11 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. )

[0073] In the above general formula (a1-2), R a11The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the formula (a) may include 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.

[0074] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0075] 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.

[0076] In n a11 When the integer is 2 or more, multiple R a11 They can be the same or different from each other.

[0077] [Chemical formula 4]

[0078]

[0079] (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. )

[0080] In the above general formula (a1-3), R a12 and R a13 The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the formula (a) may include 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 and an ethyl group are further preferred.

[0081] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0082] X in the above general formula (a1-3) a12The alkylene group having 1 to 5 carbon atoms 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.

[0083] X in the above general formula (a1-3) a12 The alkylidene group having 2 to 5 carbon atoms as 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.

[0084] In the above general formula (a1-3), n a12 and n a13 Each independently represents an integer from 0 to 4.

[0085] 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.

[0086] X in the above general formula (a1-3) a12 The divalent group represented by the general formula (a1-3-1) is as follows.

[0087] [Chemical formula 5]

[0088]

[0089] (Where R a14 and R a15 Each 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. )

[0090] In the above general formula (a1-3-1), R a14 and R a15 The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the formula (a) may include 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.

[0091] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0092] X in the above general formula (a1-3-1) a13 The alkylene group having 1 to 5 carbon atoms 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.

[0093] X in the above general formula (a1-3-1) a13 The alkylidene group having 2 to 5 carbon atoms as 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.

[0094] 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.

[0095] 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.

[0096] n a14 or a15 When the integer is 2 or more, multiple R a14 Each other or multiple R a15 They may be the same as or different from each other.

[0097] As X in the above general formula (a1-3) a12 Among the above options, preferred are an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, and a divalent group represented by the above general formula (a1-3-1), and more preferred are a divalent group represented by the above general formula (a1-3-1).

[0098] [Chemical formula 6]

[0099]

[0100] (Where R a16 and R a17 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. a16 is an integer from 1 to 8. * represents a bonding site. )

[0101] In the above general formula (a1-4), R a16 and R a17 The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the formula (a) may include an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; an alkenyl group having 2 to 5 carbon atoms; an alkynyl group having 2 to 5 carbon atoms, etc. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be straight chain or branched.

[0102] In the above general formula (a1-4), n a16 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. a16 When 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.

[0103] In the maleimide resin represented by the above general formula (a1-1), X a11 , preferably a maleimide resin having a divalent group represented by the general formula (a1-3), as X in the general formula (a1-3) a12 , more preferably a maleimide resin having a divalent group represented by the above general formula (a1-3-1).

[0104] Examples of the bismaleimide resin 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)sulfone, and bis(4-maleimidophenyl)sulfone. 1,4-bis(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)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( bis[4-(4-maleimidophenoxy)phenyl] sulfoxide, bis[4-(4-maleimidophenoxy)phenyl] sulfoxide, bis[4-(3-maleimidophenoxy)phenyl] sulfoxide, bis[4-(4-maleimidophenoxy)phenyl] sulfone, 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-maleimide phenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimide phenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimide phenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimide phenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimide phenoxy)-3,5-dimethylbenzyl]benzene methyl-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, aromatic bismaleimide having an indane skeleton, etc. Among them, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 2,2-bis[4-(4-maleimide phenoxy)phenyl]propane, and bis(4-maleimide phenyl)methane are preferred.

[0105] The description of the polymaleimide resin preferred as the maleimide resin (a1) is the same as the description of the "(B) maleimide resin having three or more N-substituted maleimide groups" described later, and the preferred aspects are also the same.

[0106] (derived from the structure of the amine compound (a2))

[0107] The structure derived from the amine compound (a2) is preferably a structure obtained by Michael addition reaction between at least one amino group of the amine compound (a2) and the N-substituted maleimide group of the maleimide resin (a1).

[0108] The structure derived from the amine compound (a2) contained in the (A) modified maleimide resin may be one kind alone or two or more kinds.

[0109] The content of the structure derived from the amine compound (a2) in the (A) modified maleimide resin is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass.

[0110] When the content of the structure derived from the amine compound (a2) in the (A) modified maleimide resin is within the above range, dielectric properties, heat resistance, flame retardancy and glass transition temperature tend to be further improved.

[0111] [Amine compound (a2)]

[0112] The amine compound (a2) is not particularly limited as long as it is an amine compound having one or more amino groups.

[0113] The amine compound (a2) is preferably an amine compound having two or more amino groups, and more preferably a diamine compound having two amino groups. From the viewpoint of low thermal expansion, the amine compound (a2) is preferably a siloxane compound having one or more amino groups, and more preferably a siloxane compound having two or more amino groups, and further preferably a siloxane compound having two amino groups.

[0114] The amino group contained in the amine compound (a2) is preferably a primary amino group.

[0115] As the amine compound (a2), a diamine compound represented by the following general formula (a2-1) is preferred.

[0116] [Chemical formula 7]

[0117] H2N-X a21 -NH2 (a2-1)

[0118] (Where X a21 is a divalent organic group.)

[0119] X in the above general formula (a2-1) a21 Preferred is a divalent group represented by the following general formula (a2-2).

[0120] [Chemical formula 8]

[0121]

[0122] (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 (a2-2-1) or the following general formula (a2-2-2). a21 and n a22 Each independently represents an integer of 0 to 4. * represents a bonding site. )

[0123] [Chemical formula 9]

[0124]

[0125] (Where R a23 and R a24 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a23It is 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. )

[0126] [Chemical formula 10]

[0127]

[0128] (Where R a25 , 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. )

[0129] As R in the above general formula (a2-2), the above general formula (a2-2-1) and the above general formula (a2-2-2) a21 , R a22 , R a23 , R a24 and R a25 The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the formula (a) may include 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 and an ethyl group are further preferred.

[0130] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0131] As X in the above general formula (a2-2) a22 , X in the above general formula (a2-2-1) a23 And X in the above general formula (a2-2-2) a24 and X a25 The alkylene group having 1 to 5 carbon atoms 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.

[0132] As X in the above general formula (a2-2) a22, X in the above general formula (a2-2-1) a23 , and X in the above general formula (a2-2-2) a24 and X a25 The alkylidene group having 2 to 5 carbon atoms as shown in the above formula 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.

[0133] In the above general formula (a2-2), 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.

[0134] 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.

[0135] In the above general formula (a2-2-1), 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.

[0136] 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.

[0137] In the above general formula (a2-2-2), 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.

[0138] n a25 When the integer is 2 or more, multiple R a25 They may be the same as or different from each other.

[0139] In addition, X in the above general formula (a2-1) a21 It may be a divalent group having a structure represented by the following general formula (a2-3), or it may be a divalent group represented by the following general formula (a2-4).

[0140] [Chemical formula 11]

[0141]

[0142] (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. )

[0143] [Chemical formula 12]

[0144]

[0145] (Where R a26 and R a27 and R in the above general formula (a2-3) a26 and R a27 Same, 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. )

[0146] As R in the above general formulae (a2-3) and (a2-4) a26 ~R a29 The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the formula (a) may include 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.

[0147] As R a26 ~R a29 The substituent of the phenyl group in the substituted phenyl group shown above may be the above-mentioned aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0148] As X a26 and X a27 Examples of the divalent organic group 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.

[0149] 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.

[0150] Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms.

[0151] Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms.

[0152] Examples of the arylene group include arylene groups having 6 to 20 carbon atoms, such as phenylene and naphthylene.

[0153] Among them, as X a26 and X a27 , preferably an alkylene group and an arylene group, and more preferably an alkylene group.

[0154] n a26 It 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.

[0155] Examples of the amine compound (a2) 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'-diaminodiphenyl sulfone, -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( Aromatic diamine compounds such as bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone and 9,9-bis(4-aminophenyl)fluorene; siloxane compounds having two amino groups, etc.

[0156] In addition, in this specification, an "aromatic diamine compound" means a compound which has two amino groups directly bonded to an aromatic ring.

[0157] Among them, from the viewpoint of excellent solubility in organic solvents, reactivity, heat resistance, dielectric properties and low water absorption, the amine compound (a2) 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)]dianiline, and 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline, and 3,3'-diethyl-4,4'-diaminodiphenylmethane is more preferred. In addition, from the viewpoint of low thermal expansion, a siloxane compound having two primary amino groups is preferred.

[0158] As the siloxane compound having two primary amino groups, a siloxane compound having primary amino groups at both terminals is preferred.

[0159] The primary amino group equivalent of the siloxane 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.

[0160] The equivalent ratio (Ta2 / Ta1) of the total equivalent weight (Ta2) of the groups derived from the amino group of the amine compound (a2) in the (A) modified maleimide resin to the total equivalent weight (Ta1) of the groups derived from the N-substituted maleimide group of the maleimide resin (a1) 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 amino group of the amine compound (a2) also include the amino group itself. In addition, the above-mentioned groups derived from the N-substituted maleimide group of the maleimide resin (a1) also include the N-substituted maleimide group itself.

[0161] ((A) Method for producing modified maleimide resin)

[0162] (A) The modified maleimide resin can be produced, for example, by reacting a maleimide resin (a1) and an amine compound (a2) in an organic solvent.

[0163] By reacting the maleimide resin (a1) and the amine compound (a2), the (A) modified maleimide resin obtained by Michael addition reaction of the maleimide resin (a1) and the amine compound (a2) can be obtained.

[0164] When the maleimide resin (a1) and the amine compound (a2) are reacted, a reaction catalyst may be used as necessary.

[0165] 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.

[0166] 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.

[0167] However, these reaction conditions can be appropriately adjusted according to the types of raw materials used, and are not particularly limited.

[0168] ((A) Content of modified maleimide resin)

[0169] In the resin composition of the present embodiment, the content of the (A) modified maleimide resin is not particularly limited, but is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of the present embodiment.

[0170] If the content of (A) modified maleimide resin is above the above lower limit, there is a tendency that heat resistance, formability, processability and conductor adhesion are easily improved. In addition, if the content of (A) modified maleimide resin is below the above upper limit, there is a tendency that dielectric properties are easily improved.

[0171] Here, in this specification, the "resin component" refers to a resin and a compound that forms a resin by a curing reaction.

[0172] For example, in the resin composition of the present embodiment, the (A) component and the (B) component correspond to the resin component.

[0173] When the resin composition of the present embodiment contains a resin or a compound that forms a resin by a curing reaction as an optional component in addition to the above components, these optional components are also included in the resin component. As an optional component equivalent to the resin component, there can be mentioned the component (C) and the component (D) described later.

[0174] On the other hand, the component (E) and the component (F) are not contained in the resin component.

[0175] The total content of the resin components in the resin composition of the present embodiment is not particularly limited, but is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and further preferably 20 to 40% by mass, relative to the total solid content (100% by mass) of the resin composition of the present embodiment.

[0176] <(B) Polymaleimide resin>

[0177] (B) The polymaleimide resin is not particularly limited as long as it is a maleimide resin having three or more N-substituted maleimide groups.

[0178] (B) The polymaleimide resin may be used alone or in combination of two or more.

[0179] The resin composition of the present embodiment contains the component (B), so that the desmear resistance of the cured product becomes excellent. The detailed reason is not clear, but one of the reasons is speculated to be that the cross-linked structure of the cured product formed by the resin composition containing the component (B) has a more complex three-dimensional structure, and the desmear treatment liquid is not easy to penetrate, or the molecules are entangled with each other to inhibit dissolution.

[0180] From the viewpoint of handling properties, the number of N-substituted maleimide groups in the polymaleimide resin (B) may be 6 or less, 5 or less, or 4 or less.

[0181] From the viewpoints of desmear resistance, heat resistance, low thermal expansion and elastic modulus, the polymaleimide resin (B) is preferably a maleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring.

[0182] The maleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring may or may not have an N-substituted maleimide group bonded to a site other than the aromatic ring.

[0183] As the (B) polymaleimide resin, a compound represented by the following general formula (B-1) is preferred.

[0184] [Chemical formula 13]

[0185]

[0186] (Where X B1 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, n B1 is an integer from 2 to 5.)

[0187] As X in the above general formula (B-1) B1 Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include divalent aliphatic hydrocarbon groups such as alkylene groups having 1 to 5 carbon atoms and alkylidene groups having 2 to 5 carbon atoms; and divalent hydrocarbon groups including aromatic hydrocarbon groups represented by the following general formula (B-2).

[0188] Examples of the alkylene group having 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc. The alkylene group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and still more preferably a methylene group.

[0189] 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 an isopropylidene group is further preferred.

[0190] [Chemical formula 14]

[0191] *-X B2 -Ar B1 -X B3 -* (B-2)

[0192] (Where Ar B1 is a divalent aromatic hydrocarbon group, X B2 and X B3 Each independently represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms. * represents a bonding site. )

[0193] As X in the above general formula (B-2) B2 and X B3 The divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by B1 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms are the same groups as mentioned above. Among them, the methylene group is preferred.

[0194] As Ar in the above general formula (B-2) B1 The divalent aromatic hydrocarbon group shown in the formula (a) may include, for example, phenylene, naphthylene, biphenylene, anthrylene, etc. Among them, biphenylene is preferred. Examples of biphenylene include 4,2'-biphenylene, 4,3'-biphenylene, 4,4'-biphenylene, 3,3'-biphenylene, etc., among which 4,4'-biphenylene is preferred.

[0195] In the above options, X in the above general formula (B-1) B1 An alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms is preferred, a methylene group or an isopropylidene group is more preferred, and a methylene group is further preferred.

[0196] In the above general formula (B-1), n B1It is an integer of 2-5, preferably an integer of 2-4, and more preferably 2 or 3.

[0197] Examples of the compound represented by the general formula (B-1) include polyphenylmethane maleimide and biphenyl aralkyl maleimide. Among them, polyphenylmethane maleimide is preferred from the viewpoints of desmear resistance, heat resistance, low thermal expansion and elastic modulus.

[0198] ((B) Content of polymaleimide resin)

[0199] The content of the (B) polymaleimide resin in the resin composition of the present embodiment is not particularly limited, but is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, further preferably 20 to 70% by mass, and particularly preferably 30 to 65% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of the present embodiment.

[0200] If the content of the (B) polymaleimide resin is above the above lower limit, there is a tendency that the desmear resistance, heat resistance, low thermal expansion and elastic modulus are easily improved. In addition, if the content of the (B) polymaleimide resin is below the above upper limit, there is a tendency that the fluidity of the resin composition is improved and the moldability is easily improved.

[0201] The ratio of the content of the component (B) to the content of the component (A) [component (B) / component (A)] is preferably 0.4 to 10, more preferably 0.6 to 7, and even more preferably 0.8 to 5 on a mass basis.

[0202] If the content ratio [(B) component / (A) component] is above the above lower limit, there is a tendency that the desmear resistance, heat resistance, low thermal expansion and elastic modulus are easily improved. In addition, if the content ratio [(B) component / (A) component] is below the above upper limit, there is a tendency that the fluidity of the resin composition is improved and the moldability is easily improved.

[0203] <(C) Epoxy resin>

[0204] The resin composition of the present embodiment preferably further contains (C) an epoxy resin.

[0205] The resin composition of the present embodiment has excellent heat resistance due to the inclusion of the (C) epoxy resin, and there is a tendency that the conductor adhesion is likely to be further improved.

[0206] (C) The epoxy resin may be used alone or in combination of two or more.

[0207] (C) 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.

[0208] (C) Epoxy resins are classified into various types according to the difference in their main skeletons.

[0209] 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 naphthalene structure are preferred from the viewpoint of heat resistance.

[0210] The epoxy group equivalent of the epoxy resin (C) is not particularly limited, but is preferably 80 to 600 g / mol, more preferably 100 to 400 g / mol, and further preferably 120 to 300 g / mol from the viewpoint of heat resistance and conductor adhesion.

[0211] ((C) Epoxy resin content)

[0212] When the resin composition of the present embodiment contains (C) epoxy resin, the content of the (C) epoxy resin in the resin composition of the present embodiment is not particularly limited, and is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 10 to 35% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of the present embodiment from the viewpoints of desmear resistance, heat resistance, low thermal expansion, elastic modulus, and conductor adhesion.

[0213] <(D) Curing agent>

[0214] The resin composition of the present embodiment preferably further contains (D) a curing agent.

[0215] The resin composition of the present embodiment tends to have better desmear resistance and heat resistance by containing the (D) curing agent.

[0216] (D) The curing agent may be used alone or in combination of two or more.

[0217] (D) curing agent includes, for example, aromatic amines such as dicyandiamide, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-diaminodiphenyl sulfone, phenylenediamine, and xylene diamine; aliphatic amines such as hexamethylenediamine and 2,5-dimethylhexamethylenediamine; guanamine compounds such as melamine and benzoguanamine; phenol resins such as phenol novolac, cresol novolac, phenol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, and aminotriazine phenol resin; benzoxazine compounds such as PD type benzoxazine; anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride, and maleic anhydride copolymers, etc. Among them, aromatic amines and benzoxazine compounds are preferred.

[0218] ((D)Content of curing agent)

[0219] When the resin composition of the present embodiment contains (D) a curing agent, the content of the (D) curing agent in the resin composition of the present embodiment is not particularly limited, and is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and further preferably 10 to 30% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of the present embodiment from the viewpoints of desmear resistance, heat resistance, low thermal expansion, elastic modulus, and conductor adhesion.

[0220] <(E) Curing Accelerator>

[0221] The resin composition of the present embodiment preferably further contains (E) a curing accelerator.

[0222] The resin composition of the present embodiment contains the (E) curing accelerator, whereby the curability is improved, and there is a tendency that more excellent dielectric properties, heat resistance, and conductor adhesion are easily obtained.

[0223] (E) The curing accelerator may be used alone or in combination of two or more.

[0224] (E) curing accelerators include, 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;

[0225] ((E) Content of curing accelerator)

[0226] When the resin composition of the present embodiment contains (E) a curing accelerator, the content of the (E) curing accelerator in the resin composition of the present embodiment is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 1% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of the present embodiment, from the viewpoint of easily obtaining a moderate curing speed.

[0227] <(F) Inorganic filler>

[0228] The resin composition of the present embodiment preferably further contains (F) an inorganic filler.

[0229] The resin composition of the present embodiment tends to easily obtain more excellent low thermal expansion property and heat resistance by containing the (F) inorganic filler.

[0230] (F) The inorganic filler may be used alone or in combination of two or more.

[0231] (F) 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.

[0232] 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.

[0233] (F) 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 (F) inorganic filler, it is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm.

[0234] It should be noted that in this specification, (F) the average particle size of the inorganic filler (D 50 ) refers to the particle diameter corresponding to the point of 50% volume when the total volume of the particles is taken as 100% and the cumulative frequency distribution curve based on the particle diameter is obtained. (F) The average particle diameter of the inorganic filler can be measured, for example, using a particle size distribution measuring device using a laser diffraction scattering method.

[0235] Examples of the shape of the (F) inorganic filler include spherical shapes and crushed shapes, and a spherical shape is preferred.

[0236] The resin composition of the present embodiment may contain a coupling agent for the purpose of improving the dispersibility of the (F) inorganic filler and the adhesion between the (F) inorganic filler and the organic component. Examples of the coupling agent include silane coupling agents and titanate coupling agents.

[0237] ((F) Content of inorganic filler)

[0238] When the resin composition of the present embodiment contains (F) an inorganic filler, the content of the (F) inorganic filler in the resin composition of the present embodiment is not particularly limited, and is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and further preferably 60 to 80% by mass, relative to the total solid content (100% by mass) of the resin composition, from the viewpoint of low thermal expansion, heat resistance, formability and conductor adhesion.

[0239] <Other ingredients>

[0240] The resin composition of the present embodiment may further contain one or more arbitrary components selected from resin materials other than the above-mentioned components, flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, silane coupling agents, organic solvents and additives other than these, as needed.

[0241] The above-mentioned optional components may be used alone or in combination of two or more.

[0242] 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.

[0243] In addition, the resin composition of the present embodiment may not contain the above-mentioned arbitrary components depending on the desired performance.

[0244] (Organic Solvent)

[0245] The resin composition of the present embodiment may contain an organic solvent from the viewpoint of easy handling and easy production of a prepreg described later.

[0246] The organic solvent may be used alone or in combination of two or more.

[0247] In addition, in this specification, the resin composition containing an organic solvent may be referred to as a resin varnish.

[0248] 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.

[0249] 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.

[0250] <Method for producing resin composition>

[0251] The resin composition of the present embodiment can be produced by mixing the above-mentioned components.

[0252] When mixing the components, the components may be dissolved or dispersed while being stirred. In addition, the order of mixing the raw materials, the mixing temperature, the mixing time and other conditions are not particularly limited and may be arbitrarily set according to the types of raw materials.

[0253] [Prepreg]

[0254] The prepreg of the present embodiment is a prepreg containing the resin composition of the present embodiment or a semi-cured product of the above-mentioned resin composition.

[0255] The prepreg of the present embodiment contains, for example, the resin composition of the present embodiment or a semi-cured product of the above-mentioned resin composition, and a sheet-like fiber base material.

[0256] As the sheet-like fiber base material contained in the prepreg of the present embodiment, for example, a known sheet-like fiber base material used in various laminated plates for electrical insulating materials can be used.

[0257] Examples of the material of the sheet-like fiber substrate include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like fiber substrates have shapes such as woven fabrics, nonwoven fabrics, rovings, chopped strand mats, and surface mats.

[0258] The prepreg of the present embodiment can be produced, for example, by impregnating or applying the resin composition of the present embodiment to a sheet-like fiber base material, followed by heating and drying to bring the material to a B-stage.

[0259] The temperature and time of heat drying are not particularly limited, and can be, for example, 50 to 200° C. and 1 to 30 minutes from the viewpoint of productivity and appropriately bringing the resin composition of the present embodiment to a B-stage.

[0260] The content of the resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and even more preferably 30 to 75% by mass, from the viewpoint of easily obtaining better formability when forming a laminate.

[0261] [Resin film]

[0262] The resin film of the present embodiment is a resin film containing the resin composition of the present embodiment or a semi-cured product of the above-mentioned resin composition.

[0263] The resin film of the present embodiment can be produced by, for example, applying the resin composition of the present embodiment containing an organic solvent, that is, a resin varnish, onto a support and then heating and drying the coating.

[0264] Examples of the support include plastic films, metal foils, and release papers.

[0265] The temperature and time of heat drying are not particularly limited, but can be set to 50 to 200° C. and 1 to 30 minutes from the viewpoint of productivity and appropriately bringing the resin composition of the present embodiment to a B-stage.

[0266] The resin film of the present embodiment is preferably used to form an insulating layer when a printed wiring board is produced.

[0267] [Laminated board]

[0268] The laminated plate of the present embodiment is a laminated plate including a cured product of the resin composition of the present embodiment and a metal foil.

[0269] In addition, the laminated plate having a metal foil is sometimes also referred to as a metal-clad laminated plate.

[0270] 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.

[0271] 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.

[0272] Usually, the laminated plate of the present embodiment is obtained by curing the B-staged prepreg through the heat and pressure molding.

[0273] In the case of heat and pressure molding, only one prepreg may be used, or two or more prepregs may be stacked.

[0274] 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.

[0275] 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.

[0276] [Printed circuit board]

[0277] The printed wiring board of the present embodiment is a printed wiring board having a cured product of the resin composition of the present embodiment.

[0278] The printed wiring board of the present embodiment can be manufactured, for example, by forming a conductor circuit on one or more of the cured product of the prepreg of the present embodiment, the cured product of the resin film of the present embodiment, and the laminate using a known method. In addition, by further performing a multilayer bonding process as required, a multilayer printed wiring board can also be manufactured. 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.

[0279] [Semiconductor package]

[0280] The semiconductor package of the present embodiment is a semiconductor package including the printed wiring board of the present embodiment and a semiconductor element.

[0281] The semiconductor package of the present embodiment can be manufactured by, for example, mounting a semiconductor chip, a memory, etc. on the printed wiring board of the present embodiment by a known method.

[0282] Example

[0283] Hereinafter, the present embodiment will be described in detail with reference to examples, but the present embodiment is not limited to the following examples.

[0284] In addition, in each example, the number average molecular weight (Mn) was measured by the following method.

[0285] 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.

[0286] Device:

[0287] Pump: L-6200 model [manufactured by Hitachi High-Technologies Co., Ltd.]

[0288] Detector: L-3300 RI [manufactured by Hitachi High-Technologies Co., Ltd.]

[0289] Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Co., Ltd.]

[0290] Column: Guard column; TSK Guardcolumn HHR-L + column; TSKgel G4000HHR + TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade names)

[0291] Column size: 6.0×40mm (guard column), 7.8×300mm (column)

[0292] Eluent: Tetrahydrofuran

[0293] Sample concentration: 30mg / 5mL

[0294] Injection volume: 20 μL

[0295] Flow rate: 1.00mL / min

[0296] Measurement temperature: 40℃

[0297] [Production Examples 1 to 5: Production of Modified Maleimide Resins AA to AE]

[0298] According to the raw material composition described in Table 1, 60 parts by mass of propylene glycol monomethyl ether and the components described in Table 1 were added to a 5-liter reaction vessel equipped with a thermometer, a stirring device, and a moisture meter with a reflux condenser, which can be heated and cooled. The obtained solution was reacted for 2 hours while refluxed, thereby obtaining solutions of modified maleimide resins AA to AE having a solid content concentration of 40% by mass. It should be noted that the units of the numerical values ​​described in the raw material composition of Table 1 are parts by mass.

[0299] Examples 1 to 10, Comparative Example 1

[0300] (Manufacture of resin composition)

[0301] The components described in Table 2 were blended according to the blending composition described in Table 2, and stirred and mixed with 58 parts by mass of toluene and 10 parts by mass of methyl isobutyl ketone at room temperature (25° C.) to produce a resin composition having a solid content concentration of 55 to 65% by mass. It should be noted that the units of the numerical values ​​described in the blending composition of Table 2 are parts by mass, and in the case of a solution, they refer to parts by mass converted to solid content.

[0302] (Manufacturing of double-sided copper-clad laminates)

[0303] The resin composition obtained above was applied to a glass fiber cloth (T glass, manufactured by Nitto Bosho Co., Ltd.) with a thickness of 0.1 mm, and then heated and dried at 130°C for 5 minutes to produce a prepreg having a content of about 50% by mass of the resin composition. Four pieces of the prepreg were overlapped, and copper foils with a thickness of 12 μm (manufactured by Mitsui Metal Industries, Ltd., trade name "3EC-M3-VLP-12", Rz of the M surface: 3.0 μm) were arranged above and below the prepreg to make the M surface contact the prepreg. The laminate was heated and pressed under the conditions of a temperature of 240°C, a pressure of 3.0 MPa, and a time of 90 minutes to produce a double-sided copper-clad laminate (thickness: 0.43 mm).

[0304] [Evaluation method]

[0305] The double-sided copper-clad laminate obtained in each example was used to perform various evaluations according to the following methods.

[0306] (Determination of Copper Foil Peel Strength)

[0307] The copper foil of the double-sided copper-clad laminate obtained in each example was processed into a straight line with a width of 3 mm 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 the copper foil peel strength was measured by peeling it in a 90° direction at room temperature (25°C) according to JIS C 6481:1996. It should be noted that the tensile speed when peeling the copper foil was set to 50 mm / min.

[0308] (Determination of glass transition temperature and thermal expansion coefficient)

[0309] The double-sided copper-clad laminate obtained in each example was immersed in a copper etching solution to remove the copper foil and prepare a 5 mm square test piece. Using the test piece, the glass transition temperature and thermal expansion coefficient were measured by a thermomechanical measuring device (TMA) [manufactured by TA Instruments Japan Co., Ltd., Q400 (model)] according to the IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard. It should be noted that the thermal expansion coefficient recorded in Table 2 is the thermal expansion coefficient in the plane direction of the plate, which refers to the value obtained by averaging the thermal expansion coefficient in the temperature range of 30 to 100°C. If the thermal expansion coefficient is 7.0ppm / °C or less, it is judged that sufficiently low thermal expansion can be obtained.

[0310] (Measurement of tensile elastic modulus E' at 50°C)

[0311] The double-sided copper-clad laminate obtained in each example was immersed in a copper etching solution to prepare a 4 mm × 40 mm test piece from which the copper foil was removed. The test piece was used to measure the tensile modulus E' at 50°C under the conditions of a span of 20 mm, a frequency of 10 Hz, and a vibration displacement of 5 μm using a wide-area viscoelasticity measuring device (DMA) [manufactured by TA Instruments Japan Co., Ltd., Q800 (model)].

[0312] (Determination of weight reduction by decontamination)

[0313] The double-sided copper-clad laminate obtained in each example is immersed in a copper etching solution to prepare a 40 mm × 40 mm evaluation substrate with the copper foil removed. The evaluation substrate is treated at 70°C for 5 minutes using a swelling treatment solution "Swelling Dip Securiganth P" (manufactured by Atotech Japan Co., Ltd.). Next, after rinsing with water at room temperature for 2 minutes, the substrate is treated at 80°C for 10 minutes or 15 minutes using a roughening solution "Concentrate Compact CP" (manufactured by Atotech Japan Co., Ltd.) for roughening. Then, after rinsing with water at 50°C for 2 minutes, the substrate is neutralized at 40°C for 5 minutes using a neutralizing solution "Reduction Solution Securiganth P500" (manufactured by Atotech Japan Co., Ltd.), and then dried after rinsing with water at room temperature for 5 minutes.

[0314] The desmearing weight reduction amount is calculated from the difference between the dry weight before the desmearing treatment and the dry weight after the desmearing treatment (dry weight before the desmearing treatment - dry weight after the desmearing treatment).

[0315] [Table 1]

[0316] Table 1

[0317]

[0318] [Table 2]

[0319] Table 2

[0320]

[0321] It should be noted that the details of the materials in Table 1 and Table 2 are as follows.

[0322] [Maleimide resin (a1) in Table 1 and component (B) in Table 2]

[0323] Polyphenylmethane maleimide: manufactured by Yamato Chemical Industry Co., Ltd., trade name "BMI-2300", a compound represented by the above general formula (B-1), X B1 For methylene.

[0324] Biphenyl aralkyl maleimide: manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-3000", a compound represented by the above general formula (B-1), X B1 X in the above general formula (B-2) B2 and X B3 is a methylene group and Ar B1 It is a divalent hydrocarbon group of 4,4'-biphenylene.

[0325] [Amine compound (a2)]

[0326] Polydimethylsiloxane having primary amino groups at both ends: manufactured by Momentive Performance Materials Japan Co., Ltd., trade name "XF42-C5379", primary amino group equivalent: 740 g / mol

[0327] [(A) ingredient]

[0328] Modified maleimide resins AA to AE: Modified maleimide resins AA to AE produced in Production Examples 1 to 5

[0329] [(C) ingredient]

[0330] Naphthol cresol novolac type epoxy resin: Epoxy equivalent: 230 g / mol, manufactured by Nippon Kayaku Co., Ltd., trade name "NC-7000L"

[0331] ·Naphthalene type epoxy resin 1: Epoxy equivalent: 250 g / mol, manufactured by DIC Corporation, trade name "HP-6000"

[0332] ·Naphthalene type epoxy resin 2: Epoxy equivalent: 143 g / mol, manufactured by DIC Corporation, trade name "HP-4032SS"

[0333] ·Naphthalene type epoxy resin 3: Epoxy equivalent: 230 g / mol, manufactured by DIC Corporation, trade name "HP-9540"

[0334] ·Naphthalene type epoxy resin 4: manufactured by DIC Corporation, trade name "EXA-7311-G4"

[0335] [(D) ingredient]

[0336] Pd-type benzoxazine: 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine)

[0337] [(E) ingredient]

[0338] ·G-8009L: Addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole

[0339] [(F)INGREDIENT]

[0340] ·Fused silica; average particle size (D 50 ): 0.5μm

[0341] The results shown in Table 2 show that the cured products formed from the resin compositions of Examples 1 to 10 of the present embodiment have a smaller desmear weight reduction than the cured product formed from the resin composition of Comparative Example 1 not containing the component (B), and are excellent in desmear resistance.

[0342] Industrial Applicability

[0343] The cured product produced from the resin composition of this embodiment has excellent desmear resistance, and therefore, prepregs, laminates, printed wiring boards, semiconductor packages, etc. obtained using the resin composition are particularly suitable for use in electronic components that process high-frequency signals.

Claims

1. A resin composition comprising: (A) a resin comprising a structure derived from a maleimide resin (a) having one or more N-substituted maleimide groups and a structure derived from an amine compound (b) having one or more amino groups, and (B) A maleimide resin having three or more N-substituted maleimide groups.

2. The resin composition according to claim 1, wherein The amine compound (b) having one or more amino groups is a siloxane compound having one or more amino groups.

3. The resin composition according to claim 1, wherein The component (B) is a maleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring.

4. The resin composition according to claim 3, wherein The maleimide resin having three or more N-substituted maleimide groups bonded to an aromatic ring is a maleimide resin represented by the following general formula (B-1): In formula (B-1), X B1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, n B1 An integer from 2 to 5.

5. The resin composition according to claim 4, wherein X in the general formula (B-1) B1 It is an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.

6. The resin composition according to any one of claims 1 to 5, wherein The ratio of the content of the component (B) to the content of the component (A), ie, component (B) / component (A), is 0.4 to 10 on a mass basis. 7 . The resin composition according to claim 1 , further comprising (C) an epoxy resin. 8 . A prepreg comprising the resin composition according to claim 1 or a semi-cured product of the resin composition. 9 . A laminate comprising a cured product of the resin composition according to claim 1 and a metal foil. 10 . A resin film comprising the resin composition according to claim 1 or a semi-cured product of the resin composition. 11 . A printed wiring board comprising a cured product of the resin composition according to claim 1 .

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

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