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

Abstract

The present invention relates to a resin composition containing (A) a thermosetting resin, (B) one or more substances selected from conjugated diene polymers and derivatives thereof and having two or more functional groups containing an ethylenically unsaturated bond, and (C) an inorganic filler surface-treated with a silane coupling agent having a functional group containing an ethylenically unsaturated bond, also provided are a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package using the resin composition.

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] The signals used in mobile communication devices such as mobile phones, their base station devices, network infrastructure devices such as servers and routers, and electronic devices such as large computers are becoming faster and larger year by year. In line with this, the substrate materials of printed circuit boards installed in these electronic devices are required to have dielectric properties that can reduce the transmission loss of high-frequency signals, namely, low relative dielectric constant and low dielectric loss tangent.

[0003] For printed circuit boards, heat resistance and mechanical properties that can be tolerated in the use environment are required, and thermosetting resins with excellent properties are used. However, most thermosetting resins contain polar groups, so it is difficult to improve the dielectric properties. Therefore, in printed circuit boards that require a high degree of low transmission loss, low-polarity polymers with excellent dielectric properties are used together with thermosetting resins.

[0004] Patent document 1 aims to provide a resin composition having low dielectric constant, low dielectric loss tangent, excellent processability and adhesion, and discloses a resin composition containing (A) a polyimide resin, (B) a phenylene ether resin, and (C) a polybutadiene resin, characterized in that the (B) phenylene ether resin contains at least one crosslinking functional group selected from a phenolic hydroxyl group, an acrylic group, a vinyl group, and an epoxy group at the end of its molecular chain, and the (C) polybutadiene resin has a number average molecular weight of 500 to 5000.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2022-063409 Summary of the invention

[0008] Problems to be solved by the invention

[0009] However, the inventors have found that when a polymer having excellent dielectric properties such as polybutadiene is added, the thermal expansion coefficient of the cured product of the resin composition increases. Therefore, it is difficult to achieve both excellent dielectric properties and low thermal expansion.

[0010] In view of the above situation, the present embodiment aims to provide a resin composition having excellent dielectric properties and low thermal expansion, and a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package using the resin composition.

[0011] Means for solving problems

[0012] As a result of conducting studies to solve the above-mentioned problems, the present inventors have found that the problems can be solved by the following present embodiment.

[0013] [1] A resin composition comprising:

[0014] (A) Thermosetting resin,

[0015] (B) at least one substance selected from conjugated diene polymers and derivatives thereof, having two or more functional groups containing ethylenically unsaturated bonds,

[0016] (C) An inorganic filler whose surface is treated with a silane coupling agent having a functional group containing an ethylenically unsaturated bond.

[0017] [2] The resin composition according to [1] above, wherein

[0018] The component (A) is one or more selected from a maleimide resin having one or more N-substituted maleimide groups and a derivative of the maleimide resin.

[0019] [3] The resin composition according to [1] or [2], wherein

[0020] The component (B) has a vinyl group as the ethylenically unsaturated bond-containing functional group.

[0021] [4] The resin composition according to any one of [1] to [3] above, wherein

[0022] The silane coupling agent having a functional group containing an ethylenically unsaturated bond has a vinyl group or a (meth)acryloyl group as the functional group containing an ethylenically unsaturated bond.

[0023] [5] The resin composition according to any one of [1] to [4], wherein

[0024] The component (C) is silica surface-treated with the silane coupling agent having a functional group containing an ethylenically unsaturated bond.

[0025] [6] The resin composition according to any one of [1] to [5], further comprising (D) a styrene-based thermoplastic resin.

[0026] [7] The resin composition according to any one of [1] to [6], further comprising (E) a curing accelerator.

[0027] [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.

[0028] [9] A laminate comprising a cured product of the resin composition according to any one of [1] to [7] above and a metal foil.

[0029]

[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.

[0030]

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

[0031]

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

[11] above and a semiconductor element.

[0032] Effects of the Invention

[0033] According to the present embodiment, it is possible to provide a resin composition having excellent dielectric properties and low thermal expansion, and a prepreg, a laminate, a resin film, a printed wiring board, and a semiconductor package using the resin composition. DETAILED DESCRIPTION

[0034] In the present specification, a numerical range expressed by "to" means a range including the numerical values ​​described before and after "to" as the minimum value and the maximum value, respectively.

[0035] 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. In addition, 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.

[0036] The lower limit value and the upper limit value of the numerical range described in the present specification can be arbitrarily combined with the lower limit value or the upper limit value of other numerical ranges, respectively.

[0037] 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.

[0038] Each component and material exemplified in the present specification may be used alone or in combination of two or more unless otherwise specified.

[0039] In the present specification, when there are plural substances corresponding to each component in the resin composition, unless otherwise specified, the content of each component in the resin composition means the total amount of the plural substances present in the resin composition.

[0040] In this specification, "solid content" refers to components other than the solvent, and components that are liquid at 25°C are also regarded as solid content.

[0041] In this specification, "(meth)acrylate" means "acrylate" and its corresponding "methacrylate". Similarly, "(meth)acrylic acid" means "acrylic acid" and its corresponding "methacrylic acid", and "(meth)acryloyl" means "acryloyl" and its corresponding "methacryloyl".

[0042] The number average molecular weight (Mn) and weight average molecular weight (Mw) in this specification refer to the values ​​measured by gel permeation chromatography (GPC) using polystyrene conversion. Specifically, the number average molecular weight (Mn) and weight average molecular weight (Mw) in this specification can be measured by the method described in the Examples.

[0043] In the present specification, the "semi-cured product" is synonymous with the resin composition in the B-stage state in JIS K 6800 (2006), and the "cured product" is synonymous with the resin composition in the C-stage state in JIS K 6800 (2006).

[0044] The mechanism of action described in this specification is a speculation and is not intended to limit the mechanism for achieving the effects of the present embodiment.

[0045] Any combination of the matters described in this specification is also included in the embodiments of the present application.

[0046] [Resin composition]

[0047] The resin composition of the present embodiment is a resin composition containing the following (A), (B), and (C):

[0048] (A) Thermosetting resin,

[0049] (B) at least one substance selected from conjugated diene polymers and derivatives thereof, having two or more functional groups containing ethylenically unsaturated bonds,

[0050] (C) An inorganic filler whose surface is treated with a silane coupling agent having a functional group containing an ethylenically unsaturated bond.

[0051] In addition, in this specification, each component may be abbreviated as (A) component, (B) component, etc., respectively, and the same abbreviation may be adopted for other components.

[0052] <(A) Thermosetting resin>

[0053] Examples of the thermosetting resin (A) include epoxy resins, phenolic resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. Among them, the thermosetting resin (A) is preferably one or more selected from epoxy resins, cyanate resins, and maleimide resins, more preferably maleimide resins, and further preferably one or more selected from maleimide resins having one or more N-substituted maleimide groups and derivatives of the maleimide resins (hereinafter also referred to as "maleimide-based resins") from the viewpoint of heat resistance and conductor adhesion.

[0054] (A) Thermosetting resins may be used alone or in combination of two or more.

[0055] 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)".

[0056] In addition, 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".

[0057] (Maleimide resin (AX))

[0058] The maleimide resin (AX) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups.

[0059] The maleimide resin (AX) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups, and more preferably an aromatic bismaleimide resin having two N-substituted maleimide groups, from the viewpoint of conductor adhesion and heat resistance.

[0060] It should be noted that the "aromatic maleimide resin" in this specification refers to a compound having an N-substituted maleimide group directly bonded to an aromatic ring. In addition, the "aromatic bismaleimide resin" in this specification refers to a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. In addition, the "aromatic polymaleimide resin" in this specification refers to a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring. In addition, the "aliphatic maleimide resin" in this specification refers to a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0061] As the maleimide resin (AX), a maleimide resin represented by the following general formula (A-1) is preferred.

[0062]

Chemical formula 1

[0063]

[0064] (Where X A1 It is a divalent organic group.

[0065] X in the above general formula (A-1) A3 It is a divalent organic group.

[0066] As X in the above general formula (A-1) A1 The divalent organic group represented by the following general formula (A-2) includes, for example, a divalent organic group represented by the following general formula (A-3), a divalent organic group represented by the following general formula (A-4), a divalent organic group represented by the following general formula (A-5), a divalent organic group represented by the following general formula (A-6), a divalent organic group represented by the following general formula (A-7), etc.

[0067]

Chemical formula 2

[0068]

[0069] (Where R A1 It is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A1 is an integer from 0 to 4. * indicates a bonding site. )

[0070] As R in the above general formula (A-2) A1 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by , for example, includes 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; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be straight chain or branched.

[0071] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0072] In the above general formula (A-2), n A1 It is 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. A1 When the integer is 2 or more, multiple R A1 They can be the same or different.

[0073]

Chemical formula 3

[0074]

[0075] (Where R A2 and R A3 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A2 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 organic group represented by the following general formula (A-3-1). A2 and n A3 Each independently represents an integer of 0 to 4. * represents a bonding site. )

[0076] As R in the above general formula (A-3) A2 and R A3 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by the above R A1 Same group.

[0077] As X in the above general formula (A-3) A2 The alkylene group having 1 to 5 carbon atoms represented by alkylene group may include, for example, 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.

[0078] As X in the above general formula (A-3) A2 Examples of the alkylidene group having 2 to 5 carbon atoms include ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and isopentylidene.

[0079] In the above general formula (A-3), n A2 and n A3 Each independently represents an integer from 0 to 4.

[0080] n A2 or A3 When the integer is 2 or more, multiple R A2 Each other or multiple R A3 They can be the same as or different from each other.

[0081] X in the above general formula (A-3) A2 The divalent organic group represented by the general formula (A-3-1) is as follows.

[0082]

Chemical formula 4

[0083]

[0084] (Where R A4 and R A5Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A3 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. A4 and n A5 Each independently represents an integer of 0 to 4. * represents a bonding site. )

[0085] As R in the above general formula (A-3-1) A4 and R A5 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by the above R A1 Same group.

[0086] As X in the above general formula (A-3-1) A3 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X include the above A2 Same group.

[0087] In the above general formula (A-3-1), n A4 and n A5 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.

[0088] n A4 or A5 When the integer is 2 or more, multiple R A4 Each other or multiple R A5 They can be the same as or different from each other.

[0089]

Chemical formula 5

[0090]

[0091] (where n A6 is an integer from 0 to 10. * indicates a bonding site. )

[0092]

Chemical formula 6

[0093]

[0094] (where n A7 It is a number from 0 to 5. * indicates a bonding site. )

[0095]

Chemical formula 7

[0096]

[0097] (Where R A6 and R A7 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.A8 is an integer from 1 to 8. * indicates a bonding site. )

[0098] As R in the above general formula (A-6) A6 and R A7 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by the above R A1 Same group.

[0099] In the above general formula (A-6), n A8 When the integer is 2 or more, multiple R A6 Each other or multiple R A7 They can be the same as or different from each other.

[0100]

Chemical formula 8

[0101]

[0102] (Where R A8 is: an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group or a mercapto group, n A9 is an integer from 0 to 3. A9 ~R A11 Each R is independently an alkyl group having 1 to 10 carbon atoms. A12 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a mercapto group. A10 Each independently represents an integer from 0 to 4, and n A11 It is a value between 0.95 and 10.0. * indicates the bonding part. )

[0103] As R in the above general formula (A-7) A8 Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc. These alkyl groups may be linear or branched.

[0104] As R A8 Examples of the alkyl group contained in the alkoxy group having 1 to 10 carbon atoms and the alkylthio group having 1 to 10 carbon atoms include the same groups as those mentioned above for the alkyl group having 1 to 10 carbon atoms.

[0105] As R A8 Examples of the aryl group having 6 to 10 carbon atoms include phenyl and naphthyl.

[0106] As R A8 Examples of the aryl group contained in the aryloxy group having 6 to 10 carbon atoms and the arylthio group having 6 to 10 carbon atoms include the same groups as those mentioned above for the aryl group having 6 to 10 carbon atoms.

[0107] As R A8 Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.

[0108] As R A9 ~R A11 The alkyl group having 1 to 10 carbon atoms represented by A8 The same group. A9 ~R A11 An alkyl group having 1 to 4 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is further preferred.

[0109] In the above general formula (A-7), n A9 is an integer from 0 to 3, where n A9 When it is 2 or 3, multiple R A8 They can be the same or different.

[0110] Among the above, the divalent organic group represented by the general formula (A-7) is preferably n A9 0, R A9 ~R A11 A divalent organic group which is a methyl group.

[0111] In the above general formula (A-7), a plurality of R A8 Each other, multiple R A12 Each other, multiple n A9 Each other, multiple n A10 They can be the same or different from each other. A11 When more than 1, multiple R A9 Each other, multiple R A10 Each other and multiple R A11 They can be the same as or different from each other.

[0112] In the above general formula (A-7), R A12 The explanations of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the alkylthio group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms, the arylthio group having 6 to 10 carbon atoms, and the cycloalkyl group having 3 to 10 carbon atoms represented by R are the same as those for the above R. A8The same as the descriptions of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the alkylthio group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, the aryloxy group having 6 to 10 carbon atoms, the arylthio group having 6 to 10 carbon atoms and the cycloalkyl group having 3 to 10 carbon atoms.

[0113] Among them, R A12 From the viewpoint of compatibility with other resins, solvent solubility, dielectric properties, adhesion to conductors and ease of production, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred.

[0114] In the above general formula (A-7), n A10 It is an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 2, from the viewpoint of compatibility with other resins, solvent solubility, dielectric properties, adhesion to a conductor, and ease of production.

[0115] In the above general formula (A-7), n A11 From the viewpoint of compatibility with other resins, solvent solubility, melt viscosity, handling properties, and heat resistance, the molecular weight is preferably 0.98 to 8.0, more preferably 1.0 to 7.0, and even more preferably 1.1 to 6.0.

[0116] The divalent organic group represented by the above-mentioned general formula (A-7) can preferably be listed as: a divalent organic group represented by the following general formula (A-7-1), a divalent organic group represented by the following general formula (A-7-2), a divalent organic group represented by the following general formula (A-7-3), a divalent organic group represented by the following general formula (A-7-4), etc.

[0117]

[0118] (where n A11 Same as in the above general formula (A-7). * indicates a bonding site. )

[0119] In the maleimide resin represented by the above general formula (A-1), X A1 Preferably, a maleimide resin having a divalent organic group represented by the above general formula (A-3) (hereinafter also referred to as "maleimide resin (i)"), or a maleimide resin having a divalent organic group represented by the above general formula (A-7) (hereinafter also referred to as "maleimide resin (ii)") is used, and it is more preferable to use maleimide resin (i) and maleimide resin (ii) in combination.

[0120] When the maleimide resin (i) and the maleimide resin (ii) are used in combination, the content ratio of the maleimide resin (i) to the maleimide resin (ii) [(i):(ii)] is not particularly limited, but from the viewpoint of dielectric properties and low thermal expansion, it is preferably 2:98 to 60:40, more preferably 5:95 to 50:50, and even more preferably 10:90 to 40:60 on a mass basis.

[0121] Examples of the maleimide resin (AX) include aromatic bismaleimide resins, aromatic polymaleimide resins, aliphatic maleimide resins, and the like. Among them, aromatic bismaleimide resins are preferred.

[0122] Specific examples of the maleimide resin (AX) include bis(4-maleimidephenyl)methane, metaphenylene bismaleimide, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 4-methyl-1,3-phenylene bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, biphenyl aralkyl maleimide, aromatic bismaleimide resins having an indane skeleton, etc. Among them, bis(4-maleimidephenyl)methane and aromatic bismaleimide resins having an indane skeleton are preferred.

[0123] (Maleimide resin derivative (AY))

[0124] The maleimide resin derivative (AY) is preferably a resin containing a structure derived from a maleimide resin having one or more N-substituted maleimide groups (i.e., the maleimide resin (AX)) and a structure derived from a diamine compound (hereinafter, sometimes also referred to as an "aminomaleimide resin").

[0125] Examples of the structure derived from the maleimide resin (AX) contained in the aminomaleimide resin include a structure in which at least one of the N-substituted maleimide groups contained in the maleimide resin (AX) undergoes a Michael addition reaction with an amino group contained in a diamine compound.

[0126] The structure derived from the maleimide resin (AX) contained in the aminomaleimide resin may be one kind alone or two or more kinds.

[0127] Examples of the structure derived from the diamine compound contained in the aminomaleimide resin include a structure in which one or both of the two amino groups contained in the diamine compound and the N-substituted maleimide group contained in the maleimide resin (AX) undergo Michael addition reaction.

[0128] The structure derived from the diamine compound contained in the aminomaleimide resin may be a single type or two or more types.

[0129] The amino group contained in the diamine compound is preferably a primary amino group.

[0130] As the diamine compound, an aromatic diamine compound having two amino groups directly bonded to an aromatic ring and an organosilicon compound having two primary amino groups are preferred.

[0131] Examples of the aromatic diamine compound include 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]dianiline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline, and 3,3'-diethyl-4,4'-diaminodiphenylmethane.

[0132] ((A) Content of thermosetting resin)

[0133] The content of the (A) thermosetting resin in the resin composition of the present embodiment is not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 20 to 40% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of the present embodiment.

[0134] When the content of the thermosetting resin (A) is above the above lower limit, the heat resistance, formability, processability and conductor adhesion tend to be improved. In addition, when the content of the thermosetting resin (A) is below the above upper limit, the dielectric properties tend to be improved.

[0135] Here, the "resin component" in this specification refers to a resin and a compound that forms a resin by a curing reaction.

[0136] In the resin composition of the present embodiment, for example, the (A) component, the (B) component, and the (D) component correspond to the resin component.

[0137] When the resin composition of the present embodiment contains a resin or a compound that forms a resin by a curing reaction as an arbitrary component in addition to the above-mentioned components, these arbitrary components are also included in the resin component.

[0138] On the other hand, the component (C) and the component (E) are not included in the resin component.

[0139] The content of the resin component in the resin composition of the present embodiment is not particularly limited, but is preferably 10 to 70% by mass, more preferably 20 to 60% 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.

[0140] When the content of the resin component is above the above lower limit, heat resistance, formability, processability and conductor adhesion tend to become better. In addition, when the content of the resin component is below the above upper limit, low thermal expansion tends to become better.

[0141] The content of the maleimide resin in the (A) thermosetting resin is not particularly limited, but is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, relative to the total amount (100% by mass) of the (A) thermosetting resin.

[0142] When the content of maleimide resin is above the above lower limit, heat resistance, formability, processability and conductor adhesion tend to be improved. In addition, when the content of maleimide resin is below the above upper limit, dielectric properties tend to be improved.

[0143] <(B) One or more selected from conjugated diene polymers and derivatives thereof, having two or more ethylenically unsaturated bond-containing functional groups>

[0144] The resin composition of the present embodiment has excellent dielectric properties by containing the component (B).

[0145] The component (B) may be used alone or in combination of two or more.

[0146] It should be noted that, in the present specification, "ethylenically unsaturated bond" refers to a carbon-carbon double bond capable of undergoing an addition reaction, excluding double bonds of an aromatic ring.

[0147] Hereinafter, in the present specification, a functional group containing an ethylenically unsaturated bond may be referred to as an "ethylenically unsaturated group".

[0148] Examples of the ethylenically unsaturated group possessed by the component (B) include vinyl, allyl, 1-methylallyl, isopropenyl, 2-butenyl, 3-butenyl, styryl, N-substituted maleimide, (meth)acryloyl, etc. Among them, the component (B) preferably has a vinyl or N-substituted maleimide as the functional group containing an ethylenically unsaturated bond, and more preferably has a vinyl as the functional group containing an ethylenically unsaturated bond.

[0149] Hereinafter, as the component (B), a conjugated diene polymer having two or more functional groups containing ethylenically unsaturated bonds (hereinafter also referred to as “(B1) conjugated diene polymer”) and a substance having two or more functional groups containing ethylenically unsaturated bonds as a derivative of the (B1) conjugated diene polymer (hereinafter also referred to as “(B1) modified conjugated diene polymer”) are described in detail.

[0150] ((B1) conjugated diene polymer)

[0151] In this specification, the "conjugated diene polymer" refers to a polymer of a conjugated diene compound.

[0152] Examples of the conjugated diene compound as a monomer component of the conjugated diene polymer (B1) include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene.

[0153] The (B1) conjugated diene polymer may be a polymer of one conjugated diene compound or a copolymer of two or more conjugated diene compounds.

[0154] The (B1) conjugated diene polymer may be a copolymer of one or more conjugated diene compounds and one or more monomers other than the conjugated diene compound.

[0155] When the conjugated diene polymer (B1) is a copolymer, the polymerization method is not particularly limited, and any of random polymerization, block polymerization, and graft polymerization may be used.

[0156] As the conjugated diene polymer (B1), a conjugated diene polymer having a vinyl group in a side chain is preferred from the viewpoint of compatibility with other resins and dielectric properties.

[0157] The number of side chain vinyl groups in one molecule of the conjugated diene polymer (B1) is not particularly limited, but is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more, from the viewpoint of compatibility with other resins and dielectric properties.

[0158] The upper limit of the number of side-chain vinyl groups in one molecule of the conjugated diene polymer (B1) is not particularly limited, and may be, for example, 100 or less, 80 or less, or 60 or less.

[0159] As (B1) conjugated diene polymer, for example: polybutadiene with 1,2-vinyl group, butadiene-styrene copolymer with 1,2-vinyl group, etc. can be cited. Among them, from the viewpoint of dielectric properties and heat resistance, polybutadiene with 1,2-vinyl group and butadiene-styrene copolymer with 1,2-vinyl group are preferred, and polybutadiene with 1,2-vinyl group is more preferred. In addition, as polybutadiene with 1,2-vinyl group, polybutadiene homopolymer with 1,2-vinyl group is preferred.

[0160] The 1,2-vinyl group derived from butadiene in the conjugated diene polymer (B1) refers to a vinyl group contained in the structural unit derived from butadiene represented by the following formula (B1-1).

[0161]

Chemical formula 9

[0162]

[0163] In the case where (B1) conjugated diene polymer is a polybutadiene with 1,2-vinyl, relative to all structural units from the butadiene constituting the polybutadiene, the content of the structural unit with 1,2-vinyl [hereinafter, also referred to as "vinyl content"] is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties and heat resistance, preferably more than 50 mol%, more preferably more than 70 mol%, further preferably more than 85 mol%. In addition, the upper limit of vinyl content is not particularly limited, and can be less than 100 mol%, can also be less than 95 mol%, can also be less than 90 mol%. As the structural unit with 1,2-vinyl, the structural unit from butadiene shown in the preferred above-mentioned formula (B1-1).

[0164] From the same viewpoint, the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.

[0165] ((B2) Modified conjugated diene polymer)

[0166] (B2) The modified conjugated diene polymer is a polymer obtained by modifying a conjugated diene polymer.

[0167] The resin composition of the present embodiment tends to easily obtain more excellent dielectric properties while having good heat resistance and low thermal expansion due to the inclusion of the (B2) modified conjugated diene polymer.

[0168] As the (B2) modified conjugated diene polymer, from the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion, it is preferably a modified conjugated diene polymer obtained by modifying a conjugated diene polymer having a vinyl group in a side chain with a maleimide resin having two or more N-substituted maleimide groups (hereinafter also referred to as "modified maleimide resin").

[0169] As the conjugated diene polymer having a vinyl group in a side chain, the conjugated diene polymer having a vinyl group in a side chain described as the (B1) conjugated diene polymer can be used, and preferred embodiments are also the same.

[0170] The conjugated diene polymer having a vinyl group in a side chain may be used alone or in combination of two or more.

[0171] As the maleimide resin for modification, for example, the maleimide resin having two or more N-substituted maleimide groups described as the component (A) can be used, and the preferred embodiments are also the same.

[0172] The modifying maleimide resin may be used alone or in combination of two or more.

[0173] The modified conjugated diene polymer (B2) preferably has a substituent formed by reacting a side chain vinyl group of a conjugated diene polymer having a vinyl group in a side chain with an N-substituted maleimide group of a maleimide resin for modification [hereinafter, sometimes referred to as a "substituent derived from a maleimide resin"] in a side chain, and more preferably has a substituent derived from a maleimide resin and a vinyl group in a side chain. In this case, the modified conjugated diene polymer (B2) is a substance having an N-substituted maleimide group and a vinyl group as ethylenically unsaturated groups.

[0174] From the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, the substituent derived from the maleimide resin is preferably a group comprising a structure represented by the following general formula (B2-1) or (B2-2) as a structure derived from a maleimide resin having two or more N-substituted maleimide groups.

[0175]

Chemical formula 10

[0176]

[0177] (Where X B21 A divalent group obtained by removing two N-substituted maleimide groups from a maleimide resin having two or more N-substituted maleimide groups, * B21 This is a site that bonds to a carbon atom of a side chain vinyl group derived from a conjugated diene polymer having a vinyl group in the side chain.* B22It is the site where atoms bond to other atoms.)

[0178] The extent to which the groups derived from the modifying maleimide resin are present in the (B2) modified conjugated diene polymer can be determined by the extent to which the vinyl groups of the conjugated diene polymer having vinyl groups in the side chains are modified by the modifying maleimide resin (hereinafter sometimes referred to as “vinyl modification ratio”).

[0179] The vinyl modification rate is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, it is preferably 20 to 70%, more preferably 30 to 60%, and further preferably 35 to 50%. Here, the vinyl modification rate is a value obtained by the method described in the Examples.

[0180] The reaction conditions of the conjugated diene polymer (B1) and the modifying maleimide resin are not particularly limited. For example, the raw materials and an organic solvent may be placed in a reaction vessel and reacted with heating and stirring as necessary to obtain the modified conjugated diene polymer (B2).

[0181] When the above reaction is carried out, the molar number (M) of the N-substituted maleimide group of the maleimide resin for modification is m ) relative to the molar number of the side chain vinyl groups of the conjugated diene polymer having the side chain vinyl groups (M v ) ratio (M m / M v ) is not particularly limited, but is preferably 0.001 to 0.5, more preferably 0.005 to 0.1, and further preferably 0.008 to 0.05 from the viewpoint of compatibility of the obtained (B2) modified conjugated diene polymer with other resins and suppression of gelation of the product in the reaction.

[0182] The number average molecular weight (Mn) of the component (B) is not particularly limited, but is preferably 700 to 6,000, more preferably 800 to 5,000, and even more preferably 1,000 to 2,500 from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance.

[0183] The content of the component (B) 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 amount (100% by mass) of the resin components in the resin composition of the present embodiment.

[0184] When the content of the component (B) is at least the above lower limit, the dielectric properties tend to be more favorable. When the content of the component (B) is at most the above upper limit, the heat resistance and flame retardancy tend to be more favorable.

[0185] <(C) Inorganic filler surface-treated with a silane coupling agent having a functional group containing an ethylenically unsaturated bond>

[0186] The resin composition of the present embodiment contains an inorganic filler material surface-treated with a silane coupling agent having a functional group containing an ethylenically unsaturated bond (hereinafter, also referred to as a "silane coupling agent") as component (C), thereby becoming a material having excellent dielectric properties and low thermal expansion. The reason is not clear, but it is speculated as follows.

[0187] The resin combination of the present embodiment contains (C) component and has been surface treated with the silane coupling agent with ethylenically unsaturated groups.Therefore, the ethylenically unsaturated groups present on the surface of (C) component become easy to react with the ethylenically unsaturated groups that (B) component has, and the crosslinking points of (B) component and (C) component increase.As a result, the thermal expansion of (B) component with relatively high thermal expansion coefficient is constrained by crosslinking with (C) component with relatively low thermal expansion coefficient, and the thermal expansion coefficient of the entire cured product is reduced.In addition, ethylenically unsaturated groups are low due to polarity, and then just enough as long as they are present on the surface of inorganic filler material, therefore it is estimated that its influence on dielectric properties is little, and dielectric properties can be well maintained.

[0188] (C) The component may be used alone or in combination of two or more.

[0189] As inorganic fillers, for example, silica, alumina, titanium oxide, mica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, calcium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, etc. can be cited. Among them, from the viewpoint of low thermal expansion, heat resistance and flame retardancy, silica, alumina, mica, talc are preferred, silica, alumina are more preferred, and silica is further preferred. That is, component (C) is preferably silica surface-treated with a silane coupling agent having a functional group containing an ethylenically unsaturated bond. As silica, fused silica is preferred from the viewpoint of dispersibility and formability.

[0190] As the ethylenically unsaturated group possessed by the silane coupling agent, for example: vinyl, allyl, 1-methylallyl, isopropenyl, 2-butenyl, 3-butenyl, styryl, N-substituted maleimide, (methyl) acryloyl, etc. can be cited. Among them, from the viewpoint of dielectric properties and low thermal expansion, the silane coupling agent preferably has vinyl or (methyl) acryloyl as a functional group containing an ethylenically unsaturated bond, and more preferably has vinyl as a functional group containing an ethylenically unsaturated bond. In addition, the ethylenically unsaturated group possessed by the silane coupling agent is preferably the same as the ethylenically unsaturated group possessed by the (B) component, and more preferably the silane coupling agent and the (B) component used for the surface treatment of the inorganic filler all have vinyl as an ethylenically unsaturated group.

[0191] The number of ethylenically unsaturated groups in one molecule of the silane coupling agent is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0192] As the silane coupling agent having an ethylenically unsaturated group, for example, silane coupling agents having a vinyl group as an ethylenically unsaturated group such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl methyl dimethoxysilane, and vinyl methyl diethoxysilane; silane coupling agents having a (meth) acryloxy group as an ethylenically unsaturated group such as γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl triethoxysilane, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyl diethoxysilane, γ-acryloxypropyl trimethoxysilane, γ-acryloxypropyl triethoxysilane, γ-acryloxypropyl methyl dimethoxysilane, and γ-acryloxypropyl methyl diethoxysilane, etc. Among them, from the viewpoint of dielectric properties and low thermal expansion, a silane coupling agent having a vinyl group is preferred.

[0193] The silane coupling agent having an ethylenically unsaturated group may be used alone or in combination of two or more.

[0194] The surface treatment method of the inorganic filler using a silane coupling agent having an ethylenically unsaturated group can be a known method. Specifically, for example, a method of treating the surface of the inorganic filler using a silane coupling agent having an ethylenically unsaturated group in a dry or wet manner can be mentioned.

[0195] (C) The average particle size of the component (D 50 ) is not particularly limited, but from the viewpoint of the dispersibility and fine wiring properties of the component (C), 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.

[0196] It should be noted that, in this specification, the average particle size (D 50 ) refers to the particle size corresponding to the point of 50% volume when the total volume of the particles is set as 100% to obtain the cumulative frequency distribution curve based on the particle size. The average particle size of the component (C) can be measured, for example, by a particle size distribution measuring device using a laser diffraction scattering method.

[0197] Examples of the shape of the component (C) include a spherical shape and a crushed shape, and a spherical shape is preferred.

[0198] The content of the component (C) in the resin composition of the present embodiment is not particularly limited, but is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 60% by mass relative to the total solid content (100% by mass) of the resin composition.

[0199] When the content of the component (C) is above the lower limit, the low thermal expansion and heat resistance tend to be improved. In addition, when the content of the component (C) is below the upper limit, the formability and conductor adhesion tend to be improved.

[0200] <(D) Styrene-based thermoplastic resin>

[0201] The resin composition of the present embodiment preferably further contains (D) a styrene-based thermoplastic resin.

[0202] The resin composition of the present embodiment tends to have further excellent dielectric properties due to the inclusion of (D) a styrene-based thermoplastic resin.

[0203] (D) The styrene-based thermoplastic resin may be used alone or in combination of two or more.

[0204] (D) The styrene-based thermoplastic resin is not particularly limited as long as it is a thermoplastic resin having a structural unit derived from a styrene-based compound.

[0205] (D) Styrene-based thermoplastic resins have structural units derived from styrene-based compounds. Examples of styrene-based compounds include styrene, alkyl-substituted styrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. The number of carbon atoms in the alkyl group of the alkyl-substituted styrene is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

[0206] (D) The styrene-based thermoplastic resin may contain a structural unit other than the structural unit derived from a styrene-based compound.

[0207] Examples of the structural unit other than the structural unit derived from the styrene-based compound that the (D) styrene-based thermoplastic resin may contain include a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, and a structural unit derived from maleic anhydride.

[0208] The structural unit derived from butadiene and the structural unit derived from isoprene may be hydrogenated. When hydrogenated, the structural unit derived from butadiene becomes a structural unit in which ethylene units and butene units are mixed, and the structural unit derived from isoprene becomes a structural unit in which ethylene units and propylene units are mixed.

[0209] (D) As a styrene-based thermoplastic resin, a hydrogenated product of a styrene-butadiene-styrene block copolymer, a hydrogenated product of a styrene-isoprene-styrene block copolymer, a styrene-maleic anhydride copolymer, etc. are mentioned, for example.

[0210] The hydrogenated product of styrene-butadiene-styrene block copolymer includes SEBS obtained by completely hydrogenating the carbon-carbon double bonds in the butadiene block and SBBS obtained by partially hydrogenating the carbon-carbon double bonds in the 1,2-bonding portion of the butadiene block. The hydrogenated product of styrene-isoprene-styrene block copolymer is obtained as SEPS by hydrogenating the polyisoprene portion. Among them, SEBS and SEPS are preferred from the viewpoints of dielectric properties, conductor adhesion, heat resistance, glass transition temperature and low thermal expansion, and SEBS is more preferred.

[0211] In the (D) styrene-based thermoplastic resin, the content of the structural unit derived from the styrene-based compound [hereinafter sometimes referred to as "styrene content"] is not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass from the viewpoint of dielectric properties, conductor adhesion, heat resistance, glass transition temperature and low thermal expansion.

[0212] The weight average molecular weight (Mw) of the (D) styrene-based thermoplastic resin is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 350,000, and even more preferably 60,000 to 200,000.

[0213] When the resin composition of the present embodiment contains (D) a styrene-based thermoplastic resin, the content of the (D) styrene-based thermoplastic resin is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of the present embodiment.

[0214] When the content of the (D) styrene-based thermoplastic resin is at least the above lower limit, the dielectric properties tend to be more favorable. When the content of the (D) styrene-based thermoplastic resin is at most the above upper limit, the heat resistance and flame retardancy tend to be more favorable.

[0215] ((E) Curing accelerator)

[0216] The resin composition of the present embodiment preferably further contains (E) a curing accelerator.

[0217] The resin composition of the present embodiment contains the (E) curing accelerator, thereby improving curability and tends to easily obtain more excellent dielectric properties, heat resistance, and conductor adhesion.

[0218] (E) The curing accelerator may be used alone or in combination of two or more.

[0219] (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, 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and isocyanate-masked imidazole; quaternary ammonium compounds; triphenylphosphine, as an addition reaction of p-benzoquinone and tri-n-butylphosphine; Phosphorus compounds such as quaternary phosphonium compounds of the product; 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, α,α'-bis(tert-butylperoxy)diisopropylbenzene; inorganic peroxides; azo compounds; carboxylates of manganese, cobalt, zinc, etc.; acidic catalysts such as p-toluenesulfonic acid, etc. Among them, organic peroxides and imidazole compounds are preferred, and α,α'-bis(tert-butylperoxy)diisopropylbenzene and isocyanate-masked imidazoles are more preferred, and their combination is further preferred.

[0220] When the resin composition of the present embodiment contains (E) a curing accelerator, the content of the (E) curing accelerator is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 6 parts by mass, relative to 100 parts by mass of the (A) thermosetting resin.

[0221] When the content of the curing accelerator (E) is at least the above lower limit, a sufficient curing acceleration effect tends to be easily obtained. In addition, when the content of the curing accelerator (E) is at most the above upper limit, the storage stability tends to be further improved.

[0222] <(F) Flame retardant>

[0223] The resin composition of the present embodiment preferably further contains (F) a flame retardant.

[0224] The resin composition of the present embodiment tends to have further improved flame retardancy due to the inclusion of the (F) flame retardant.

[0225] (F) The flame retardant may be used alone or in combination of two or more. A flame retardant auxiliary may be contained as necessary.

[0226] (F) As a flame retardant, a phosphorus flame retardant, a metal hydrate, a halogen flame retardant, etc. are mentioned, for example.

[0227] Examples of the halogen flame retardant include chlorine flame retardants and bromine flame retardants. Among them, bromine flame retardants are preferred.

[0228] ((F) Content of flame retardant)

[0229] When the resin composition of the present embodiment contains (F) a flame retardant, the content of the (F) flame retardant is not particularly limited, but from the viewpoint of flame retardancy and moldability, it is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 30 to 40 parts by mass relative to 100 parts by mass of the total of the resin components in the resin composition of the present embodiment.

[0230] <Other ingredients>

[0231] The resin combination of the present embodiment may further contain one or more of the additives selected from the resin material, antioxidant, heat stabilizer, antistatic agent, ultraviolet absorber, pigment, colorant, lubricant and these other than the above-mentioned components as required. For each of these additives, one may be used alone, or two or more may be used in combination. In addition, their usage is not particularly limited, and may be used as required within the scope of not affecting the effect of the present embodiment.

[0232] (Organic Solvent)

[0233] 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.

[0234] The organic solvent may be used alone or in combination of two or more.

[0235] 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.

[0236] Among them, alcohol solvents, ketone solvents, nitrogen atom-containing solvents, and aromatic hydrocarbon solvents are preferred from the viewpoint of solubility, ketone solvents are more preferred, and methyl ethyl ketone is further preferred.

[0237] <Method for producing resin composition>

[0238] The resin composition of the present embodiment can be manufactured by mixing the components in a known manner. At this time, the components can be dissolved or dispersed while stirring. The conditions such as the mixing order, temperature, and time are not particularly limited and can be arbitrarily set according to the types of raw materials.

[0239] [Prepreg]

[0240] 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.

[0241] The prepreg of the present embodiment includes, 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.

[0242] As the sheet-like fiber base material contained in the prepreg of the present embodiment, for example, a known sheet-like fiber base material that can be used for various laminated plates for electrical insulating materials can be used.

[0243] 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.

[0244] The prepreg of the present embodiment can be produced by, for example, 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 base material into a B-stage.

[0245] The temperature and time of heat drying are not particularly limited, but can be set to, for example, 50 to 200° C. and 1 to 30 minutes from the viewpoint of productivity and appropriately B-stage the resin composition of the present embodiment.

[0246] 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.

[0247] [Resin film]

[0248] 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.

[0249] 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 onto a support and then heating and drying the coating.

[0250] Examples of the support include plastic films, metal foils, and release papers.

[0251] 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 making the resin composition of the present embodiment appropriately B-staged.

[0252] The resin film of the present embodiment is preferably used to form an insulating layer when a printed wiring board is produced.

[0253] [Laminated board]

[0254] 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.

[0255] In addition, the laminated plate having a metal foil is sometimes also referred to as a metal-clad laminated plate.

[0256] 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.

[0257] 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 and pressure molding.

[0258] Usually, the laminated plate of the present embodiment is obtained by curing the B-staged prepreg through the heat and pressure molding.

[0259] In the case of heat and pressure molding, only one prepreg may be used, or two or more prepregs may be stacked and used.

[0260] 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.

[0261] 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.

[0262] [Printed circuit board]

[0263] 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.

[0264] 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, 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.

[0265] [Semiconductor package]

[0266] The semiconductor package of the present embodiment is a semiconductor package including the printed wiring board of the present embodiment and a semiconductor element.

[0267] 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 using a known method.

[0268] Example

[0269] Hereinafter, the present embodiment will be described in detail with reference to examples, but the present embodiment is not limited to the following examples.

[0270] In addition, in each example, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured in the following procedure.

[0271] (Method for measuring number average molecular weight (Mn) and weight average molecular weight (Mw))

[0272] The number average molecular weight (Mn) and the weight average molecular weight (Mw) are converted by gel permeation chromatography (GPC) based on a calibration curve using standard polystyrene. The calibration curve is approximated by a cubic formula using standard polystyrene: TSK standard POLYSTYRENE (model: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name]. The measurement conditions of GPC are shown below.

[0273] Device: High-speed GPC device HLC-8320GPC

[0274] Detector: UV-8320 ultraviolet absorption detector [manufactured by Tosoh Corporation]

[0275] Column: Guard column: TSK Guardcolumn SuperHZ-L + Column: TSKgel SuperHZM-N + TSKgel SuperHZM-M + TSKgel Super H-RC (all manufactured by Tosoh Corporation, trade names)

[0276] Column size: 4.6×20mm (guard column), 4.6×150mm (column), 6.0×150mm (reference column)

[0277] Eluent: Tetrahydrofuran

[0278] Sample concentration: 10mg / 5mL

[0279] Injection volume: 25 μL

[0280] Flow rate: 1.00mL / min

[0281] Measurement temperature: 40℃

[0282] (Determination of vinyl modification rate)

[0283] The liquid containing the conjugated diene polymer and the modified maleimide resin before the reaction and the liquid containing the modified conjugated diene polymer obtained after the reaction were used as the measurement objects, and the GPC measurement was performed under the above conditions. The reduction rate of the peak area from the modified maleimide resin before and after the reaction, that is, (the peak area from the modified maleimide resin before the reaction-the peak area from the modified maleimide resin after the reaction)×100 / (the peak area from the modified maleimide resin before the reaction) was obtained, and the obtained value was taken as the vinyl modification rate.

[0284] [Manufacturing of modified conjugated diene polymer]

[0285] Production Example 1

[0286] Into a 2L glass flask container equipped with a thermometer, a reflux condenser and a stirring device capable of heating and cooling, 33.5 parts by mass of 1,2-polybutadiene homopolymer (number average molecular weight = 1,200, vinyl content = 85% or more) as a conjugated diene polymer, 1.48 parts by mass of 4,4'-diphenylmethane bismaleimide as a maleimide resin for modification, 0.034 parts by mass of α,α'-bis(tert-butylperoxy)diisopropylbenzene as an organic peroxide, and toluene as an organic solvent were added, and stirred and reacted at 90 to 100° C. under a nitrogen atmosphere for 5 hours to obtain a liquid containing a modified conjugated diene polymer (toluene diluted liquid, solid content concentration: 35% by mass). The obtained modified conjugated diene polymer had a vinyl modification rate of 40% and a number average molecular weight (Mn) of 1,900.

[0287] [Manufacturing of resin composition]

[0288] Examples 1 to 5, Comparative Examples 1 to 4

[0289] According to the formulation described in Table 1, each component described in Table 1 was stirred and mixed with methyl ethyl ketone at room temperature to prepare a resin composition having a solid content concentration of 55% by mass. It should be noted that the unit of the amount of each component in Table 1 is part by mass, and in the case of a solution, it refers to the part by mass converted to the solid content.

[0290] The varnish obtained above was applied to a glass cloth having a thickness of 0.08 mm, and then heated and dried at 105° C. for 4 minutes to produce a prepreg having a content of about 75% by mass of the resin composition. A low-profile copper foil having a thickness of 18 μm was arranged above and below the prepreg in such a manner that the M surface (matte surface) was in contact with the prepreg, and then heated and pressed at a temperature of 190° C., a pressure of 3.0 MPa, and a time of 80 minutes to produce a double-sided copper-clad laminate (thickness: 0.60 mm).

[0291] [Evaluation method]

[0292] The double-sided copper-clad laminate obtained in each example was used to perform various measurements and evaluations according to the following methods.

[0293] (Measurement method of relative dielectric constant (Dk) and dielectric loss tangent (Df))

[0294] The double-sided copper-clad laminate obtained in each example was immersed in a 10 mass % solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a copper etching liquid, to remove the copper foil on both sides, thereby preparing a 2 mm × 50 mm test piece. Next, based on the cavity resonator perturbation method, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the above test piece were measured at an atmosphere temperature of 25°C and a frequency band of 10 GHz.

[0295] (Method for measuring thermal expansion coefficient)

[0296] The copper foil on both sides of the double-sided copper-clad laminate obtained in each example was removed by etching to prepare a 5 mm square evaluation substrate. Next, a thermomechanical analysis was performed by compression method using a thermomechanical measuring device (TMA) (manufactured by TA Instruments Japan, Inc., trade name "Q400"). After the evaluation substrate was installed in the above-mentioned device, it was continuously measured twice under the measurement condition of a heating rate of 10°C / min. It should be noted that the thermal expansion coefficient is the thermal expansion coefficient in the thickness direction of the laminate, and the average thermal expansion coefficient α1 in the temperature range of 30 to 120°C and the average thermal expansion coefficient α2 in the temperature range of 250 to 300°C were obtained in the second measurement.

[0297]

Table 1

[0298] Table 1

[0299]

[0300] In addition, the details of each material described in Table 1 are as follows.

[0301] [(A) ingredient]

[0302] Maleimide resin 1: Aromatic bismaleimide resin containing indane ring

[0303] Maleimide resin 2: 4,4'-diphenylmethane bismaleimide

[0304] [(B) ingredient]

[0305] Modified conjugated diene polymer: the modified conjugated diene polymer obtained in Production Example 1

[0306] [(C) ingredient]

[0307] Inorganic filler 1: fused spherical silica surface-treated with a silane coupling agent having a vinyl group (average particle size of silica (D 50 ) is 0.5μm)

[0308] Inorganic filler 2: fused spherical silica surface-treated with a silane coupling agent having a methacryloyl group (average particle size of silica (D 50 ) is 0.5μm)

[0309] [(C') ingredient]

[0310] Inorganic filler 3: fused spherical silica surface-treated with a silane coupling agent having an amino group (average particle size of silica (D 50 ) is 0.5μm)

[0311] Inorganic filler 4: fused spherical silica surface-treated with a silane coupling agent having an epoxy group (average particle size of silica (D 50 ) is 0.5μm)

[0312] Inorganic filler 5: fused spherical silica surface-treated with a silane coupling agent having a fluoroalkyl group (average particle size of silica (D 50 ) is 0.5μm)

[0313] Inorganic filler 6: fused spherical silica surface-treated with a silane coupling agent having an alkyl group (average particle size of silica (D 50 ) is 0.5μm)

[0314] [(D) ingredient]

[0315] Styrene-based thermoplastic resin 1: styrene-ethylene-butylene-styrene block copolymer (SEBS), "KRATON (registered trademark) MD6951" manufactured by Kraton Polymers Japan, Inc., styrene content: 34% by mass, weight average molecular weight (Mw): 150,000

[0316] Styrene-based thermoplastic resin 2: styrene-ethylene-butylene-styrene block copolymer (SEBS), "KRATON (registered trademark) MD1648" manufactured by Kraton Polymers Japan, Inc., styrene content: 20% by mass, weight average molecular weight (Mw): 70,000

[0317] [(E) ingredient]

[0318] ·α,α'-Bis(tert-butylperoxy)diisopropylbenzene

[0319] · Isocyanate-masked imidazole: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "G8009L"

[0320] [(F)INGREDIENT]

[0321] Flame retardant: Ethylene bis(pentabromophenyl), trade name "SAYTEX8010"

[0322] As can be seen from Table 1, the resin compositions of Examples 1 to 5 of the present embodiment are excellent in dielectric properties and low thermal expansion. On the other hand, the resin compositions of Comparative Examples 1 to 4 are inferior in low thermal expansion.

Claims

1. A resin composition comprising: (A) Thermosetting resin, (B) at least one substance selected from conjugated diene polymers and derivatives thereof, having two or more functional groups containing ethylenically unsaturated bonds, (C) An inorganic filler whose surface is treated with a silane coupling agent having a functional group containing an ethylenically unsaturated bond.

2. The resin composition according to claim 1, wherein The component (A) is at least one selected from a maleimide resin having at least one N-substituted maleimide group and a derivative of the maleimide resin.

3. The resin composition according to claim 1 or 2, wherein The component (B) has a vinyl group as the ethylenically unsaturated bond-containing functional group.

4. The resin composition according to claim 1 or 2, wherein The silane coupling agent having a functional group containing an ethylenically unsaturated bond has a vinyl group or a (meth)acryloyl group as the functional group containing an ethylenically unsaturated bond.

5. The resin composition according to claim 1 or 2, wherein The component (C) is silica surface-treated with the silane coupling agent having a functional group containing an ethylenically unsaturated bond. The resin composition according to claim 1 or 2, further comprising (D) a styrene-based thermoplastic resin. 7 . The resin composition according to claim 1 , further comprising (E) a curing accelerator. 8 . A prepreg comprising the resin composition according to claim 1 or 2 or a semi-cured product of the resin composition. 9 . A laminate comprising a cured product of the resin composition according to claim 1 or 2 and a metal foil. 10 . A resin film comprising the resin composition according to claim 1 or 2 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 or 2.

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

Images