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

Abstract

Provided are: a resin composition comprising (A) at least one selected from the group consisting of maleimide resins having at least one N-substituted maleimide group and derivatives thereof, (B) a conjugated diene-based polymer, and (C) an inorganic filling material, wherein the content of the (C) inorganic filling material is 5-15 vol% with respect to the total amount of solid contents of the resin composition; and a prepreg, a laminated plate, a resin film, a printed wiring board, and a semiconductor package using said resin composition.

Description

Resin compositions, prepregs, laminates, resin films, printed circuit boards, and semiconductor packages

[0001] This embodiment relates to resin compositions, prepregs, laminates, resin films, printed circuit boards, and semiconductor packages.

[0002] In mobile communication devices such as mobile phones, their base station equipment, network infrastructure equipment such as servers and routers, and electronic devices such as large computers, the speed and capacity of the signals used are increasing year by year. Along with the increase in signal speed and capacity, the substrate materials for printed circuit boards used in electronic devices are required to reduce the transmission loss of high-frequency signals.

[0003] Patent Document 1 discloses a thermosetting resin composition that has a low dielectric loss tangent, low thermal expansion, and excellent wiring embedding and flatness properties, and describes a technique for incorporating a polybutadiene elastomer modified with an acid anhydride into a thermosetting resin composition containing an inorganic filler, a polyimide compound having structural units derived from a maleimide resin having at least two N-substituted maleimide groups and structural units derived from a diamine compound.

[0004] Japanese Patent Publication No. 2018-012747

[0005] Maleimide resins, used as thermosetting resins, exhibit excellent heat resistance and other properties, but their dielectric properties still have room for improvement. One effective method for improving dielectric properties is to add low-polarity components, such as elastomers, to a resin composition containing a maleimide compound, as described in Patent Document 1. However, low-polarity components such as elastomers have poor compatibility with high-polarity maleimide compounds, which can lead to separation in the cured resin composition. Consequently, inorganic fillers in the resin composition tend to be unevenly distributed in the cured resin matrix region formed from the maleimide resin, resulting in areas of aggregated separated resin with low inorganic filler content and areas of cured resin matrix with high inorganic filler content, leading to poor homogeneity of the cured product.

[0006] In view of the current situation, this embodiment aims to provide a resin composition with excellent homogeneity of cured products, and prepregs, laminates, resin films, printed circuit boards, and semiconductor packages using the resin composition.

[0007] The present inventors have conducted studies to solve the above problems and have found that the following embodiments [1] to [9] can solve the problems. [1] A resin composition comprising: (A) one or more selected from the group consisting of maleimide resins and derivatives thereof having one or more N-substituted maleimide groups; (B) a conjugated diene polymer; and (C) an inorganic filler, wherein the content of the inorganic filler (C) is 5 to 15% by volume with respect to the total amount of solids of the resin composition. [2] The resin composition according to [1], wherein component (A) is one or more selected from the group consisting of maleimide resins and derivatives thereof having a fused ring of an aromatic ring and an aliphatic ring in its molecular structure and having two or more N-substituted maleimide groups. [3] The resin composition according to [1] or [2] above, wherein component (B) is one or more selected from the group consisting of a conjugated diene polymer having vinyl groups in its side chains and a modified conjugated diene polymer obtained by modifying a conjugated diene polymer having vinyl groups in its side chains with a maleimide resin having two or more N-substituted maleimide groups. [4] The resin composition according to any one of [1] to [3] above, wherein the inorganic filler (C) is silica. [5] A prepreg containing the resin composition according to any one of [1] to [4] above or a semi-cured product of the resin composition. [6] A laminate having a cured product of the resin composition according to any one of [1] to [4] above or a prepreg according to [5] above, and a metal foil. [7] A resin film containing the resin composition according to any one of [1] to [4] above or a semi-cured product of the resin composition. [8] A printed circuit board having a cured product of the resin composition according to any one of [1] to [4] above. [9] A semiconductor package having the printed circuit board described in [8] above and a semiconductor element.

[0008] According to this embodiment, it is possible to provide a resin composition with excellent homogeneity of cured products, and prepregs, laminates, resin films, printed circuit boards, and semiconductor packages using the resin composition.

[0009] This is a cross-sectional SEM image of the laminate manufactured in Example 1. This is a cross-sectional SEM image of the laminate manufactured in Comparative Example 1.

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

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

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

[0013] Herein, in this specification, "resin component" means resin and compounds that form resin through a curing reaction. In the resin composition of this embodiment, for example, components (A) and (B) described later correspond to the resin component. If the resin composition of this embodiment contains, as optional components, resin or compounds that form resin through a curing reaction in addition to the above components, these optional components are also included in the resin component.

[0014] The expression "contains XX" as used herein includes both the meaning of containing XX in a reacted state if XX is capable of reacting, and simply the meaning of containing XX.

[0015] In this specification, the number-average molecular weight (Mn) refers to the value measured in polystyrene equivalent by gel permeation chromatography (GPC). Specifically, the number-average molecular weight (Mn) in this specification can be measured by the method described in the examples.

[0016] In this specification, "semi-cured product" is synonymous with a resin composition in the B-stage state as defined in JIS K 6800 (2006), and "cured product" is synonymous with a resin composition in the C-stage state as defined in JIS K 6800 (2006).

[0017] The mechanism of action described herein is speculative and does not limit the mechanism by which the effects of this embodiment are achieved.

[0018] Embodiments that combine any combination of the information described herein are also included.

[0019] [Resin Composition] The resin composition of this embodiment is a resin composition comprising: (A) one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives thereof; (B) a conjugated diene polymer; and (C) an inorganic filler, wherein the content of (C) the inorganic filler is 5 to 15% by volume relative to the total solid content of the resin composition.

[0020] In this specification, each component may be referred to as "Component (A)," "Component (B)," etc., as appropriate. The components that the resin composition of this embodiment may contain will be described in order below.

[0021] <Component (A)> Component (A) is one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of said maleimide resins. Component (A) may be used alone or in combination of two or more.

[0022] In the following explanation, maleimide resins having one or more N-substituted maleimide groups may be referred to as "maleimide resin (AX)" or "(AX) component." Furthermore, derivatives of maleimide resins having one or more N-substituted maleimide groups may be referred to as "maleimide resin derivative (AY)" or "(AY) component."

[0023] (Maleimide resin (AX)) The maleimide resin (AX) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups, but from the viewpoint of conductive adhesion and heat resistance, it is preferable that it is 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.

[0024] In this specification, "aromatic maleimide resin" means a compound having an N-substituted maleimide group directly bonded to an aromatic ring. In this specification, "aromatic bismaleimide resin" means a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. In this specification, "aromatic polymaleimide resin" means a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring. In this specification, "aliphatic maleimide resin" means a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0025] As the maleimide resin (AX), a maleimide resin represented by the following general formula (A-1) is preferred.

[0026] (In the formula, X Ａ１ (It is a divalent organic group.)

[0027] X in the above general formula (A-1) Ａ１ Examples of divalent organic groups represented by the following general formulas (A-2), (A-3), (A-4), (A-5), (A-6), or (A-7) include divalent organic groups represented by the following general formulas.

[0028] (In the formula, R Ａ１ n is an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. Ａ１is an integer of 0 to 4. * represents a bonding site.)

[0029] In the above general formula (A-2), R Ａ１ Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and n-pentyl group; alkenyl groups having 2 to 5 carbon atoms; alkynyl groups 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. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. n Ａ１ is an integer of 2 or more, a plurality of R Ａ１ may be the same as or different from each other.

[0030] (In the formula, R Ａ２ and R Ａ３ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X Ａ２ is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent organic group represented by the following general formula (A-3-1). n Ａ２ and n Ａ３ are each independently an integer of 0 to 4. * represents a bonding site.)

[0031] Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R Ａ２ and R Ａ３ in the above general formula (A-3) include the same ones as the above R Ａ１ . Examples of the alkylene group having 1 to 5 carbon atoms represented by X Ａ２ in the above general formula (A-3) include a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, and the like. As the alkylene group having 1 to 5 carbon atoms, a methylene group is preferred. X in the above general formula (A-3) Ａ２Examples of alkylidene groups with 2 to 5 carbon atoms represented by include ethylidene, propyridene, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene. Ａ２ or n Ａ３ If is an integer greater than or equal to 2, then multiple R Ａ２ R with other R or multiple R Ａ３ They may be the same or they may be different.

[0032] X in the above general formula (A-3) Ａ２ The divalent organic group represented by the general formula (A-3-1) is as follows:

[0033] (In the formula, R Ａ４ and R Ａ５ Each of these is independently an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. Ａ３ This is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. Ａ４ and n Ａ５ Each of these is an independent integer between 0 and 4. (* represents a connecting point.)

[0034] In the above general formula (A-3-1), R Ａ４ and R Ａ５ The aliphatic hydrocarbon group having 1 to 5 carbon atoms and halogen atoms represented by are as follows: Ａ１ The same thing can be cited 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 are the above X Ａ２ The same thing can be cited. n in the above general formula (A-3-1) Ａ４ and n Ａ５ Each of these is an integer between 0 and 4, and from the viewpoint of availability, they are preferably integers between 0 and 2. Ａ４ or n Ａ５ If is an integer greater than or equal to 2, then multiple R Ａ４ R with other R or multiple R Ａ５ They may be the same or they may be different.

[0035] (In the formula, n Ａ６ (This is an integer between 0 and 10. * represents a connection point.)

[0036] (In the formula, n Ａ７ (The numbers are 0 to 5. * represents a connection site.)

[0037] (In the formula, R Ａ６ and R Ａ７ Each of these is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Ａ８ (This is an integer between 1 and 8. * represents a connection point.)

[0038] In the above general formula (A-6), R Ａ６ and R Ａ７ The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by the above R is Ａ１ The same thing can be cited as the above general formula (A-6) n Ａ８ If is an integer greater than or equal to 2, then multiple R Ａ６ R with other R or multiple R Ａ７ They may be the same or they may be different.

[0039] (In the formula, R Ａ８ This is an alkyl group having 1 to 10 carbon atoms, an alkyloxy 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 R is an integer between 0 and 3. Ａ９ ~R Ａ１１ Each of these is an alkyl group having 1 to 10 carbon atoms. Ａ１２ Each of these is independently a C1-C10 alkyl group, a C1-C10 alkyloxy group, a C1-C10 alkylthio group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C6-C10 arylthio group, a C3-C10 cycloalkyl group, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group. Ａ１０ Each of these is an integer from 0 to 4, and n Ａ１１The value ranges from 0.95 to 10.0. (* indicates a binding site.)

[0040] In the above general formula (A-7), R Ａ８ Examples of C1-C10 alkyl groups represented by include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. These alkyl groups may be linear or branched. Ａ８ Examples of alkyl groups included in the C1-C10 alkyloxy group and C1-C10 alkylthio group represented by the above include the same C1-C10 alkyl groups. Ａ８ Examples of aryl groups having 6 to 10 carbon atoms represented by R include the phenyl group and the naphthyl group. Ａ８ The aryl groups included in the aryloxy group and arylthio group having 6 to 10 carbon atoms represented by the above-mentioned aryl group having 6 to 10 carbon atoms are the same as those mentioned above. Ａ８ Examples of cycloalkyl groups having 3 to 10 carbon atoms represented by the formula include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups.

[0041] R Ａ９ ~R Ａ１１ The alkyl group having 1 to 10 carbon atoms represented by the above R is Ａ８ The same can be said for these. Among these, R Ａ９ ~R Ａ１１ The C1-C4 alkyl group is preferred, a methyl group and an ethyl group are more preferred, and a methyl group is even more preferred. n in the above general formula (A-7) Ａ９ n is an integer between 0 and 3. Ａ９ If there are 2 or 3, then multiple R Ａ８ They may be the same or they may be different.

[0042] Among the above, the divalent organic group represented by the general formula (A-7) is considered to have compatibility with other resins, solvent solubility, dielectric properties, adhesion to conductors, and ease of manufacture, n Ａ９ If R is 0, Ａ９~R Ａ１１ It is preferable that the group is a methyl group, which is a divalent organic group.

[0043] In the above general formula (A-7), multiple R Ａ８ fellow, multiple R Ａ１２ fellows, multiple n Ａ９ fellows, multiple n Ａ１０ Each of them may be the same or different. Also, n Ａ１１ If the number exceeds 1, multiple R Ａ９ fellow, multiple R Ａ１０ R with each other and with multiple Rs Ａ１１ Each of the members may be the same or different.

[0044] In the above general formula (A-7), R Ａ１２ For an explanation of the C1-C10 alkyl groups, C1-C10 alkyloxy groups, C1-C10 alkylthio groups, C6-C10 aryl groups, C6-C10 aryloxy groups, C6-C10 arylthio groups, and C3-C10 cycloalkyl groups represented by R, see above. Ａ８ The explanation is the same as for alkyl groups having 1 to 10 carbon atoms, alkyloxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, arylthio groups having 6 to 10 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms. Among these, R Ａ１２ From the viewpoint of compatibility with other resins, solvent solubility, dielectric properties, adhesion to conductors, and ease of manufacture, C1-C4 alkyl groups, C3-C6 cycloalkyl groups, and C6-C10 aryl groups are preferred, and C1-C3 alkyl groups are more preferred. n in the above general formula (A-7) Ａ１０ n is an integer from 0 to 4, and is preferably an integer from 0 to 3, more preferably 0 or 2, from the viewpoint of compatibility with other resins, solvent solubility, dielectric properties, adhesion to conductors, and ease of manufacture. Ａ１１ From the viewpoint of compatibility with other resins, solvent solubility, melt viscosity, handling properties, and heat resistance, the viscosity is preferably 0.98 to 8.0, more preferably 1.0 to 7.0, and even more preferably 1.1 to 6.0.

[0045] The divalent organic group represented by the above general formula (A-7) preferably includes the divalent organic group represented by the following general formula (A-7-1), the divalent organic group represented by the following general formula (A-7-2), the divalent organic group represented by the following general formula (A-7-3), the divalent organic group represented by the following general formula (A-7-4), and so on.

[0046] (In the formula, n Ａ１１ This is the same as the one in the general formula (A-7) above. (* indicates a bonding site.)

[0047] As for the maleimide resin (AX), from the viewpoint of dielectric properties, a maleimide resin that contains a fused ring of an aromatic ring and an aliphatic ring in its molecular structure and has two or more N-substituted maleimide groups is preferred. That is, component (A) is preferably one or more selected from the group consisting of maleimide resins and derivatives thereof that contain a fused ring of an aromatic ring and an aliphatic ring in their molecular structure and have two or more N-substituted maleimide groups. As for the fused ring, from the viewpoint of dielectric properties, conductor adhesion and ease of manufacture, one having a fused bicyclic structure is preferred, and an indan ring is more preferred. As for the maleimide resin having an indan ring, X in the general formula (A-1) above is preferred. Ａ１ Examples include compounds having a divalent organic group represented by the above general formula (A-7).

[0048] Examples of maleimide resins (AX) include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins, among which aromatic bismaleimide resins are preferred. Examples of maleimide resins (AX) include bis(4-maleimidophenyl)methane, m-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 4-methyl-1,3-phenylenebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, aromatic bismaleimide resins containing an indan ring, and biphenylaralkyl type maleimide resins.

[0049] Among the maleimide resins represented by the general formula (A-1) above, component (A) is preferably an aromatic bismaleimide resin containing an indan ring [hereinafter sometimes referred to as "maleimide resin (A1)"] or a maleimide resin having three or more N-substituted maleimide groups in one molecule [hereinafter sometimes referred to as "maleimide resin (A2)"]. Examples of maleimide resins having three or more N-substituted maleimide groups in one molecule include polyphenylmethanemaleimide and biphenylaralkyl type maleimide resin. When maleimide resin (A1) and maleimide resin (A2) are used in combination, the content ratio of maleimide resin (A1) to maleimide resin (A2) [(A1):(A2)] is not particularly limited, but from the viewpoint of dielectric properties and low thermal expansion, it is preferably 10:90 to 95:5 by mass, more preferably 30:70 to 90:10, even more preferably 40:60 to 85:15, and particularly preferably 50:50 to 80:20.

[0050] (Maleimide resin derivative (AY)) As the maleimide resin derivative (AY), an aminomaleimide resin having structural units derived from the maleimide resin (AX) described above and structural units derived from a diamine compound is preferred. The aminomaleimide resin has structural units derived from the maleimide resin (AX) and structural units derived from a diamine compound. The aminomaleimide resin can be obtained, for example, by Michael addition of the maleimide resin (AX) and a diamine compound. As the diamine compound, for example, one similar to the amine compound having at least two primary amino groups in one molecule as listed in Japanese Patent Application Publication No. 2020-200406 can be used. Among these, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, and 3,3'-diethyl-4,4'-diaminodiphenylmethane are preferred.

[0051] The content of component (A) in the resin composition of this embodiment is preferably 10 to 97% by mass, more preferably 30 to 95% by mass, even more preferably 50 to 92% by mass, and even more preferably 70 to 90% by mass, based on the total amount of resin components (100% by mass) in the resin composition of this embodiment. When the content of component (A) is above the lower limit, the heat resistance, moldability, processability, and conductive adhesion tend to be better. Also, when the content of component (A) is below the upper limit, the dielectric properties tend to be better.

[0052] <(B) Conjugated diene polymer> The resin composition of this embodiment further contains a (B) conjugated diene polymer. The resin composition of this embodiment tends to have better dielectric properties due to the inclusion of a (B) conjugated diene polymer. A single (B) conjugated diene polymer may be used, or two or more may be used in combination.

[0053] (B) A conjugated diene polymer is a polymer containing structural units derived from a conjugated diene compound. Examples of conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. (B) A conjugated diene polymer may be a polymer of one conjugated diene compound, or a copolymer of two or more conjugated diene compounds. Furthermore, (B) a conjugated diene polymer may be a copolymer of one or more conjugated diene compounds and one or more monomers other than conjugated diene compounds. When (B) a conjugated diene polymer is a copolymer, the polymerization method may be random polymerization, block polymerization, or graft polymerization.

[0054] (B) Conjugated diene polymers are preferably those having vinyl groups in their side chains from the viewpoint of compatibility with other resins and dielectric properties. (B) The number of side-chain vinyl groups in one molecule of a conjugated diene polymer is preferably 2 to 100, more preferably 5 to 80, and even more preferably 10 to 60, from the viewpoint of compatibility with other resins and dielectric properties.

[0055] (B) Examples of conjugated diene polymers include polybutadiene having 1,2-vinyl groups, butadiene-styrene copolymer having 1,2-vinyl groups, and modified products thereof. In polybutadiene having 1,2-vinyl groups, the content of structural units having 1,2-vinyl groups relative to the total structural units derived from butadiene constituting the polybutadiene [hereinafter sometimes referred to as "vinyl group content"] is preferably 50 to 100 mol%, more preferably 70 to 95 mol%, and even more preferably 85 to 90 mol% from the viewpoint of compatibility with other resins, dielectric properties and heat resistance.

[0056] (B) The conjugated diene polymer is preferably a modified conjugated diene polymer obtained by modifying a conjugated diene polymer having vinyl groups in its side chains with a maleimide resin having two or more N-substituted maleimide groups [hereinafter sometimes referred to as "modifying maleimide resin"], from the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion. That is, the (B) conjugated diene polymer is preferably one or more selected from the group consisting of a conjugated diene polymer having vinyl groups in its side chains and a modified conjugated diene polymer obtained by modifying a conjugated diene polymer having vinyl groups in its side chains with a maleimide resin having two or more N-substituted maleimide groups. Examples of conjugated diene polymers having vinyl groups in their side chains include polybutadiene having the above-mentioned 1,2-vinyl groups. As the modifying maleimide resin, for example, a maleimide resin having two or more N-substituted maleimide groups as described in component (A) can be used. Among these, aromatic bismaleimide resin is preferred, and in the above general formula (A-1), X Ａ１ A maleimide resin in which the divalent organic group is represented by the above general formula (A-3) is more preferred, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide is even more preferred.

[0057] The modified conjugated diene polymer preferably has, in its side chain, a substituent formed by the reaction between the side chain vinyl group of a conjugated diene polymer having a vinyl group in the side chain and the N-substituted maleimide group of a modifying maleimide resin [hereinafter sometimes referred to as "maleimide resin-derived substituent"], and more preferably has the maleimide resin-derived substituent and a vinyl group in its side chain.

[0058] From the viewpoints of compatibility with other resins, dielectric properties, low thermal expandability and heat resistance, the maleimide resin-derived substituent is preferably a group containing a structure represented by the following general formula (B-1) or (B-2) as the structure derived from the modifying maleimide resin.

[0059] (wherein, X Ｂ１ is a divalent group obtained by removing two N-substituted maleimide groups from the modifying maleimide resin, and * Ｂ１ is a site bonded to a carbon atom derived from the side chain vinyl group of the conjugated diene polymer having a vinyl group in the side chain. * Ｂ２ is a site bonded to another atom.)

[0060] The reaction conditions for the conjugated diene polymer having a vinyl group in the side chain and the maleimide resin are not particularly limited. For example, the modified conjugated diene polymer can be obtained by charging the raw materials and an organic solvent into a reaction vessel, and allowing the reaction to proceed while heating, stirring and the like as necessary.

[0061] In carrying out the above reaction, the number of moles of side chain vinyl groups possessed by the conjugated diene polymer having a vinyl group in the side chain (M ｖ ) relative to 、 the number of moles of N-substituted maleimide groups possessed by the modifying maleimide resin (M ｍ ) (M ｍ / M ｖ ) is preferably 0.0005 to 0.1, more preferably 0.001 to 0.05, and even more preferably 0.002 to 0.01, from the viewpoints of the compatibility of the modified conjugated diene polymer with other resins and suppression of gelation of the product.

[0062] (B) The number-average molecular weight (Mn) of the conjugated diene polymer is preferably 400 to 3,000, more preferably 600 to 2,000, and even more preferably 800 to 1,500, from the viewpoint of compatibility with other resins, dielectric properties and heat resistance.

[0063] The content of (B) conjugated diene polymer in the resin composition of this embodiment is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 8 to 30% by mass, and even more preferably 10 to 20% by mass, based on the total amount of resin components in the resin composition (100% by mass). When the content of (B) conjugated diene polymer is above the lower limit, the dielectric properties tend to be better. Also, when the content of (B) conjugated diene polymer is below the upper limit, the heat resistance and flame retardancy tend to be better.

[0064] <(C) Inorganic Filler> The resin composition of this embodiment further contains (C) an inorganic filler, and in the resin composition of this embodiment, the content of (C) an inorganic filler is 5 to 15 volume percent with respect to the total solid content of the resin composition of this embodiment. When the content of (C) an inorganic filler is 15 volume percent or less, the homogeneity of the cured resin composition is excellent. Also, when the content of (C) an inorganic filler is 5 volume percent or more, the low thermal expansion of the resin composition is excellent. From the above viewpoint, the content of (C) an inorganic filler is preferably 5 to 14 volume percent, more preferably 6 to 13 volume percent, with respect to the total solid content of the resin composition of this embodiment. Also, from the viewpoint of homogeneity of the cured resin composition, the content of (C) an inorganic filler may be 10 volume percent or less, or 8 volume percent or less, with respect to the total solid content of the resin composition of this embodiment.

[0065] The mass-based content of (C) inorganic filler in the resin composition of this embodiment is preferably 8 to 25% by mass, more preferably 9 to 24% by mass, even more preferably 10 to 22% by mass, even more preferably 11 to 21% by mass, and particularly preferably 12 to 20% by mass, based on the total solid content (100% by mass) of the resin composition of this embodiment.

[0066] Examples of the inorganic filler (C) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, and the like. Among these, from the viewpoints of low thermal expansibility, heat resistance and flame retardancy, silica, alumina, mica and talc are preferred, silica and alumina are more preferred, and silica is even more preferred. As the inorganic filler (C), one type may be used alone, or two or more types may be used in combination.

[0067] The average particle diameter (D ５０ ) of the inorganic filler (C) is not particularly limited, but from the viewpoints of the dispersibility and fine wiring formability of the inorganic filler (C), it is preferably 0.01 to 10 μm, more preferably 0.02 to 5 μm, even more preferably 0.03 to 1 μm, and still more preferably 0.04 to 0.8 μm. In one aspect of the present embodiment, the average particle diameter (D ５０ ) of the inorganic filler (C) is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, even more preferably 0.3 to 1 μm, and still more preferably 0.4 to 0.8 μm. In another aspect of the present embodiment, the average particle diameter (D ５０ ) of the inorganic filler (C) is preferably 10 to 500 nm, more preferably 20 to 300 nm, even more preferably 30 to 200 nm, and still more preferably 40 to 100 nm. In the present specification, the average particle diameter (D ５０ ) of the inorganic filler (C) refers to the particle diameter at the point corresponding to a volume of 50% when a cumulative frequency distribution curve based on particle diameters is determined with the total volume of the particles taken as 100%. The average particle diameter of the inorganic filler (C) can be measured, for example, with a particle size distribution measuring apparatus using a laser diffraction scattering method or the like.

[0068] (C) Examples of the shape of the inorganic filler include spherical and crushed shapes, with spherical being preferred. (C) The inorganic filler may be surface-treated with a surface treatment agent such as a silane coupling agent, for example, from the viewpoint of improving dispersibility and adhesion with organic components.

[0069] <(D) Curing Accelerator> The resin composition of this embodiment preferably further contains (D) a curing accelerator. The resin composition of this embodiment tends to have improved curability, dielectric properties, heat resistance, and conductor adhesion due to the inclusion of (D) a curing accelerator. (D) a curing accelerator may be used alone or in combination of two or more types.

[0070] (D) Examples of curing accelerators include: acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, tributylamine, pyridine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate; isocyanate mask imidazole compounds such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; quaternary ammonium compounds; triphenylphosphine, and quaternary phosphonium compounds which are the addition reaction products of p-benzoquinone and tri-n-butylphosphine. Examples include phosphorus compounds such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy)diisopropylbenzene; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile); and carboxylates of manganese, cobalt, zinc, etc. Among these, isocyanate maskimidazole compounds are preferred from the viewpoint of curing acceleration effect and storage stability.

[0071] If the resin composition of this embodiment contains (D) a curing accelerator, the content of (D) the curing accelerator is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of component (A). When the content of (D) the curing accelerator is above the lower limit, a sufficient curing acceleration effect tends to be easily obtained. Also, when the content of (D) the curing accelerator is below the upper limit, storage stability tends to be better.

[0072] <(E) Flame retardant> The resin composition of this embodiment preferably further contains (E) a flame retardant. The resin composition of this embodiment tends to have better flame retardancy when it contains (E) a flame retardant. (E) A single type of flame retardant may be used alone, or two or more types may be used in combination.

[0073] (E) Examples of flame retardants include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, etc. Among these, phosphorus-based flame retardants are preferred.

[0074] The phosphorus-based flame retardant may be an inorganic or organic phosphorus-based flame retardant, but an organic phosphorus-based flame retardant is preferred. Examples of organic phosphorus-based flame retardants include aromatic phosphate ester compounds, monosubstituted phosphonic acid diester compounds, disubstituted phosphinic acid ester compounds, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, and cyclic organophosphorus compounds. Among these, aromatic phosphate ester compounds are preferred. Examples of aromatic phosphate ester compounds include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 4,4'-biphenylene-tetrakis(2,6-dimethylphenyl) phosphate, bisphenol A-bis(diphenyl phosphate), and 1,3-phenylene bis(diphenyl phosphate). Among these, 4,4'-biphenylene-tetrakis(2,6-dimethylphenyl) phosphate ester is preferred.

[0075] If the resin composition of this embodiment contains (E) a flame retardant, the amount of (E) a flame retardant is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total amount of resin components in the resin composition. When the amount of (E) a flame retardant is above the lower limit, the flame retardancy tends to be better. Also, when the amount of (E) a flame retardant is below the upper limit, the dielectric properties, moldability, and conductor adhesion tend to be better.

[0076] <Other Optional Components> The resin composition of this embodiment may further contain other optional components as needed, such as resin materials other than the above components, flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, silane coupling agents, organic solvents, and other additives. Each of the other optional components may be used alone or in combination of two or more. The content of the above optional components in the resin composition of this embodiment is not particularly limited and may be used as needed, within a range that does not hinder the effects of this embodiment. Furthermore, the resin composition of this embodiment may not contain the above optional components depending on the desired performance. The total content of components (A), (B), and (C) in the resin composition of this embodiment is preferably 50 to 100% by mass, more preferably 70 to 99.8% by mass, and even more preferably 80 to 99.6% by mass, based on the total solid content (100% by mass) of the resin composition of this embodiment.

[0077] (Organic solvents) The resin composition of this embodiment may contain organic solvents from the viewpoint of handling. In this specification, resin compositions containing organic solvents may be referred to as resin varnishes. Examples of organic solvents include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone. Among these, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, nitrogen atom-containing solvents, and aromatic hydrocarbon-based solvents are preferred, aromatic hydrocarbon-based solvents are more preferred, and toluene is even more preferred.

[0078] [Prepreg] The prepreg of this embodiment is a prepreg containing the resin composition of this embodiment or a semi-cured product of the resin composition. Preferably, the prepreg of this embodiment contains the resin composition of this embodiment or a semi-cured product of the resin composition and a sheet-like fibrous base material.

[0079] As the sheet-like fibrous base material contained in the prepreg of this embodiment, known sheet-like fibrous base materials used in various types of laminates for electrical insulation materials can be used. Examples of materials for the sheet-like fibrous base material 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 fibrous base materials have shapes such as woven fabrics, nonwoven fabrics, rovings, chopped strand mats, and surfacing mats.

[0080] The prepreg of this embodiment can be manufactured, for example, by impregnating or coating a sheet-like fibrous substrate with the resin composition of this embodiment, and then heating and drying it to achieve a B-stage. The heating and drying temperature and time can be, for example, 50 to 200°C and 1 to 30 minutes, from the viewpoint of productivity and appropriately B-stage the resin composition of this embodiment.

[0081] The content of the resin composition in the prepreg of this embodiment 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 moldability when formed into a laminate.

[0082] The thickness of the prepreg can be adjusted as appropriate depending on the application, but from the viewpoint of moldability and workability, it is preferably 20 to 500 μm, more preferably 40 to 400 μm, even more preferably 60 to 300 μm, and even more preferably 80 to 200 μm.

[0083] [Laminate] The laminate of this embodiment is a laminate having a cured product of the resin composition of this embodiment and a metal foil. A laminate having a metal foil is sometimes called a metal-clad laminate.

[0084] The metal used for the metal foil is not particularly limited and includes, for example, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metallic elements.

[0085] The laminate of this embodiment can be manufactured, for example, by placing metal foil on one or both sides of the prepreg of this embodiment and then heat-pressure molding. Typically, the laminate of this embodiment is obtained by curing the B-staged prepreg through this heat-pressure molding. When heat-pressure molding, only one prepreg may be used, or two or more prepregs may be laminated and used. For heat-pressure molding, for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, or an autoclave molding machine can be used. The conditions for heat-pressure molding are not particularly limited, but for example, the temperature can be 100 to 300°C, the time can be 10 to 300 minutes, and the pressure can be 1.5 to 5 MPa.

[0086] [Resin Film] The resin film of this embodiment is a resin film containing the resin composition of this embodiment or a semi-cured product of the resin composition. The resin film of this embodiment can be manufactured, for example, by applying the resin composition of this embodiment containing an organic solvent to a support and then heating and drying it. Examples of support materials include plastic films, metal foils, and release paper. The heating and drying temperature and time can be set to 50 to 200°C and 1 to 30 minutes, from the viewpoint of productivity and appropriately B-stage the resin composition of this embodiment. The resin film of this embodiment is preferably used to form an insulating layer when manufacturing printed circuit boards.

[0087] [Printed Wiring Board] The printed wiring board of this embodiment is a printed wiring board having a cured product of the resin composition of this embodiment. A method for manufacturing the printed wiring board of this embodiment is, for example, a method of forming a conductive circuit on one or more laminates selected from the group consisting of a cured product of the resin composition of this embodiment, a cured product of a prepreg containing the resin composition of this embodiment and a fiber substrate, and a cured product of the resin composition of this embodiment and a metal foil. The conductive circuit can be formed by known methods, for example, by appropriately applying metal plating, etching of the metal foil, etc. Furthermore, a preferred method for manufacturing the printed wiring board of this embodiment is a method of drilling holes using a drill on one or more laminates selected from the group consisting of a cured product of the resin composition of this embodiment, a cured product of a prepreg containing the resin composition of this embodiment and a fiber substrate, and a cured product of the resin composition of this embodiment and a metal foil. Conventional known methods can be applied for drilling holes. In addition, a multilayer printed wiring board can be manufactured by further applying multilayer bonding as needed.

[0088] [Semiconductor Package] The semiconductor package of this embodiment is a semiconductor package having the printed circuit board of this embodiment and semiconductor elements. The semiconductor package of this embodiment can be manufactured, for example, by mounting semiconductor chips, memory, etc., on the printed circuit board of this embodiment by known methods.

[0089] The embodiment will be described in detail below with reference to examples. However, this embodiment is not limited to the following examples.

[0090] In each example, the number-average molecular weight (Mn) was measured using the following procedure. (Method for measuring number-average molecular weight (Mn)) The number-average molecular weight (Mn) was calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a cubic equation using standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-20, F-80) [manufactured by Tosoh Corporation, trade name]. The GPC measurement conditions are shown below. Instrument: High-speed GPC instrument HLC-8320GPC Detector: UV-8320 ultraviolet absorption detector [manufactured by Tosoh Corporation] Columns: Guard column; TSKgel guardcolumn Super(HZ)-M+ Column; TSKgel SuperMultipore HZ-M (2), Reference column; TSKgel SuperH-RC (2) (all manufactured by Tosoh Corporation, product names) Column size: 4.6 × 20 mm (guard column), 4.6 × 150 mm (column), 6.0 × 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10 mg / mL Injection volume: 20 μL or 2 μL Flow rate: 0.35 mL / min Measurement temperature: 40°C

[0091] Production Example 1 (Production of Modified Conjugated Diene Polymer) 100 parts by mass of 1,2-polybutadiene homopolymer (number average molecular weight (Mn) = 1,200, vinyl group content = 85% or more), 4.4 parts by mass of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 0.1 parts by mass of α,α'-bis(t-butylperoxy)diisopropylbenzene, and toluene as an organic solvent were added to a 2 L container capable of heating and cooling, equipped with a thermometer, reflux condenser, and stirring device. The mixture was then stirred under a nitrogen atmosphere at 90-100°C for 5 hours to obtain a solution of modified conjugated diene polymer with a solid content concentration of 35% by mass.

[0092] [Preparation of Resin Composition] Examples 1-4, Comparative Example 1 Each component listed in Table 1 was stirred and mixed with methyl ethyl ketone to prepare a varnish-like resin composition with a solid content concentration of 60% by mass. In Table 1, the unit of the amount of each component is parts by mass, and in the case of a solution, it means parts by mass on a solid content basis.

[0093] [Prepreg Manufacturing] The varnish-like resin composition obtained above is used to make glass cloth (manufactured by Nitto Boseki Co., Ltd., product name "T2118", thickness 0.098 mm, basis weight 114 g / m²). ２ A prepreg was obtained by impregnating glass (type: T glass) with the material and heating and drying it at 110°C for 3 minutes. The thickness of the obtained prepreg was 0.1 mm, and the resin composition content in the prepreg was 48.5% by mass.

[0094] [Manufacturing of Copper-Clad Laminates] Seven sheets of the prepreg obtained above were stacked, and 12 μm thick copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-M3-VLP-12", roughened surface Rz: 3.0 μm) was placed above and below the stack so that the roughened surface was in contact with the prepreg. This laminate was heated and pressurized for 90 minutes at a temperature of 240°C and a pressure of 3.0 MPa to produce a copper-clad laminate (thickness: 0.7 mm).

[0095] [Evaluation Method] The copper-clad laminates prepared in each example were evaluated according to the method described below. The results are shown in Table 1.

[0096] (Confirmation of the presence or absence of aggregation regions of the separation resin) After embedding and hardening the copper-clad laminate manufactured as described above with embedding resin, it was polished using a polishing machine (Refine Tech Co., Ltd., product name "Refine Polisher") to obtain a test specimen by cutting out the cross-section of the copper-clad laminate. Next, the cross-section of the test specimen was observed using a scanning electron microscope (SEM) (Hitachi High-Technologies Corporation, product name: SV-4700) under the conditions of secondary electron mode, acceleration voltage of 10 kV, and observation magnification of 500x to confirm the presence or absence of aggregation regions of the separation resin. The "aggregation region of the separation resin" was defined as the resin portion in the cross-sectional SEM image obtained above where the inorganic filler is not visible and the maximum diameter is 40 μm or more. Figure 1 shows a cross-sectional SEM image of the laminate manufactured in Example 1, and Figure 2 shows a cross-sectional SEM image of the laminate manufactured in Comparative Example 1. In Figure 2, the portion indicated by the arrow corresponds to the aggregation region of the separation resin.

[0097]

[0098] The details of each material in Table 1 are as follows: [Component (A)] Maleimide resin 1: Aromatic bismaleimide resin containing an indan ring, represented by the above general formula (A-1), where X Ａ１ A compound in which the divalent organic group represented by is the divalent organic group represented by the above general formula (A-7). • Maleimide resin 2: Polyphenylmethanemaleimide (manufactured by Yamato Chemical Industries, Ltd., trade name "BMI-2300") • Maleimide resin 3: Biphenyl aralkyl type maleimide (manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-3000")

[0099] [Component (B)] Modified conjugated diene polymer: Modified conjugated diene polymer synthesized in Production Example 1

[0100] [(C) Component] Silica 1: Spherical fused silica, average particle size (D ５０ ) 0.5 μm ・Silica 2: Synthetic spherical silica, average particle size (D ５０ ) 50 nm

[0101] [(D) Ingredients] - Hardening accelerator: Isocyanate macuimidazole (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name "G-8009L")

[0102] [Component (E)] Flame retardant: 4,4'-biphenylene-tetrakis(2,6-dimethylphenyl) phosphate ester

[0103] The results shown in Table 1 indicate that the cured products of the resin compositions of Examples 1 to 4 of this embodiment exhibit excellent homogeneity.

Claims

1. A resin composition comprising: (A) one or more selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives thereof; (B) a conjugated diene polymer; and (C) an inorganic filler, wherein the content of (C) the inorganic filler is 5 to 15% by volume relative to the total solid content of the resin composition.

2. The resin composition according to claim 1, wherein component (A) is one or more selected from the group consisting of maleimide resins and derivatives thereof, which contain a fused ring of an aromatic ring and an aliphatic ring in their molecular structure and have two or more N-substituted maleimide groups.

3. The resin composition according to claim 1 or 2, wherein component (B) is one or more selected from the group consisting of a conjugated diene polymer having vinyl groups in its side chains, and a modified conjugated diene polymer obtained by modifying a conjugated diene polymer having vinyl groups in its side chains with a maleimide resin having two or more N-substituted maleimide groups.

4. The resin composition according to claim 1 or 2, wherein the inorganic filler (C) is silica.

5. A prepreg containing the resin composition described in claim 1 or 2, or a semi-cured product of the resin composition.

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

7. A resin film containing the resin composition described in claim 1 or 2, or a semi-cured product of the resin composition.

8. A printed circuit board having a cured product of the resin composition according to claim 1 or 2.

9. A semiconductor package having a printed circuit board as described in claim 8 and a semiconductor element.

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