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

Abstract

This invention relates to resin compositions, prepregs using the resin compositions, laminates, resin films, printed circuit boards, and semiconductor packages, wherein the resin compositions contain: (A) one or more maleimide compounds and their derivatives, wherein the maleimide compounds contain a fused ring of aromatic and aliphatic rings in their molecular structure and have two or more N-substituted maleimide groups; and (B) a resin having a tensile modulus of elasticity of 10 GPa or less at 25°C.

Description

Technical Field

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

[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 mainframe computers, the speed and capacity of signals used are advancing year by year. Along with this, the substrate materials of the printed circuit boards used in these electronic devices require dielectric properties [hereinafter sometimes referred to as "high-frequency characteristics"] that can reduce the transmission loss of high-frequency signals, namely, low relative permittivity and low dielectric loss tangent.

[0003] In recent years, in addition to the aforementioned electronic devices, the practical application or implementation plans for new systems that process high-frequency wireless signals have been advancing in the fields of intelligent transport systems (ITS) related to automobiles and transportation systems, as well as in indoor short-range communication. Therefore, it is expected that the need for substrate materials with excellent high-frequency characteristics for printed circuit boards used in these fields will increase in the future.

[0004] Patent Document 1 discloses a thermosetting resin composition with low dielectric loss tangent, low thermal expansion, and excellent embedding and flatness of wiring. The composition contains an inorganic filler and a polyimide compound, incorporating an anhydride-modified polybutadiene elastomer. The polyimide compound has structural units derived from maleimide compounds having at least two N-substituted maleimide groups and structural units derived from diamine compounds.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2018-012747 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] However, in recent years, substrate materials have been required for use in fifth-generation mobile communication system (5G) antennas that use radio waves in frequency bands exceeding 6 GHz and in millimeter-wave radars that use radio waves in frequency bands of 30–300 GHz. Therefore, there is a need to develop resin compositions with further improved dielectric properties for frequency bands above 10 GHz.

[0010] Reducing the contact area between the insulating layer and the conductor formed on the insulating layer is also an effective method to reduce transmission loss. However, reducing the contact area between the insulating layer and the conductor may lead to a decrease in the adhesion between the insulating layer and the conductor. Therefore, it is difficult to achieve a high balance between dielectric properties and adhesion to the conductor.

[0011] While the thermosetting resin composition disclosed in Patent Document 1 has excellent dielectric properties, there is room for improvement in achieving even better dielectric properties and adhesion to conductors.

[0012] In view of this situation, the objective of this embodiment is to provide a resin composition with excellent dielectric properties and adhesion to conductors in high frequency bands above 10 GHz, a prepreg using the resin composition, a laminate, a resin film, a printed circuit board, and a semiconductor package.

[0013] Methods for solving problems

[0014] In order to solve the above-mentioned problem, the inventors conducted research and found that the problem can be solved by the following embodiment.

[0015] That is, this embodiment relates to the following [1] to

[11] .

[0016] [1] A resin composition comprising:

[0017] (A) Selected from one or more maleimide compounds and their derivatives, wherein the maleimide compound comprises a fused ring of an aromatic ring and an aliphatic ring in its molecular structure and has two or more N-substituted maleimide groups; and

[0018] (B) Resins with a tensile modulus of less than 10 GPa at 25°C.

[0019] [2] According to the resin composition described in [1] above, wherein the fused ring is an indene ring.

[0020] [3] According to the resin composition described in [2] above, the indane ring is included in the component (A) as a divalent group represented by the following general formula (a1-1).

[0021] [Chemical Formula 1]

[0022]

[0023] (where R is in the formula) a1It is an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, where n1 is an integer from 0 to 3. R a2 ~R a4 Each is an alkyl group having 1 to 10 carbon atoms. * indicates a bonding site.

[0024] [4] The resin composition according to any one of [1] to [3] above, wherein the above-mentioned component (B) contains one or more selected from polyolefin resins, polyphenylene ether resins, silicone resins and epoxy resins.

[0025] [5] According to the resin composition described in [4] above, wherein the above-mentioned component (B) contains a modified conjugated diene polymer as the above-mentioned polyolefin resin, the modified conjugated diene polymer being prepared by modifying (b1) a conjugated diene polymer having vinyl groups on the side chain with (b2) a maleimide compound having two or more N-substituted maleimide groups.

[0026] [6] According to the resin composition described in [4] or [5] above, wherein the above-mentioned component (B) contains a styrene-based elastomer as the above-mentioned polyolefin resin.

[0027] [7] A prepreg containing the resin composition described in any one of [1] to [6] above or a semi-cured product of the resin composition described above.

[0028] [8] A laminate having a cured resin composition of any one of [1] to [6] or a cured prepreg of any one of [7] and a metal foil.

[0029] [9] A resin film containing the resin composition described in any one of [1] to [6] above or a semi-cured product of the resin composition described above.

[0030]

[10] A printed circuit board having one or more of the following: a cured resin composition selected from any one of [1] to [6] above, a cured prepreg selected from [7] above, and a laminate selected from [8] above.

[0031]

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

[10] above.

[0032] Invention Effects

[0033] According to this embodiment, a resin composition with excellent dielectric properties and adhesion to conductors in high-frequency bands above 10 GHz, a prepreg using the resin composition, a laminate, a resin film, a printed circuit board, and a semiconductor package are provided. Detailed Implementation

[0034] In this specification, the numerical range indicated by “~” represents the range of minimum and maximum values ​​recorded before and after the “~”.

[0035] The lower and upper limits of the numerical ranges described in this specification can be arbitrarily combined with the lower or upper limits of other numerical ranges.

[0036] In the numerical range described in this specification, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the embodiments.

[0037] Unless otherwise specified, each component and material illustrated in this instruction manual may be used individually or in combination of two or more.

[0038] In this specification, the content of each component in the resin composition refers to the total amount of the various substances present in the resin composition, unless otherwise specified, when multiple substances corresponding to each component are present in the resin composition.

[0039] This embodiment also includes any combination of the items described in this specification.

[0040] The mechanisms of action described in this specification are speculative and are not intended to limit the mechanisms by which the resin composition of this embodiment achieves its effect.

[0041] The term "compatibility" in this specification means that the resins are not necessarily compatible at the molecular level, but are mixed together at the nanometer or micrometer level or in appearance.

[0042] In this specification, "semi-cured product" has the same meaning as resin compositions in the B-stage state in JIS K 6800 (1985), and "cured product" has the same meaning as resin compositions in the C-stage state in JIS K 6800 (1985).

[0043] The number-average molecular weight in this specification refers to the value determined by gel permeation chromatography (GPC) converted to polystyrene. Specifically, the number-average molecular weight in this specification can be determined by the methods described in the examples.

[0044] [Resin Composition]

[0045] The resin composition of this embodiment contains:

[0046] (A) is selected from one or more maleimide compounds and their derivatives, wherein the maleimide compound comprises a fused ring of an aromatic ring and an aliphatic ring in its molecular structure and has two or more N-substituted maleimide groups [hereinafter, sometimes referred to as "(A) component"].

[0047] (B) Resins with a tensile modulus of elasticity of 10 GPa or less at 25°C [hereinafter sometimes simply referred to as "tensile modulus of elasticity at 25°C"].

[0048] The reasons for the superior dielectric properties and conductor adhesion [hereinafter, sometimes referred to as "conductor adhesion"] of the resin composition of this embodiment in the high-frequency band above 10 GHz are not yet certain, but are speculated as follows.

[0049] The resin composition of this embodiment contains component (A), which is a maleimide compound with a fused ring consisting of aromatic and aliphatic rings in its molecular structure. It is believed that the inclusion of aliphatic rings with low polarity in the fused ring structure contributes to a reduction in the dielectric loss tangent of the cured product obtained from the resin composition of this embodiment, and its large three-dimensional structure contributes to a reduction in the relative permittivity. Furthermore, the fused rings in component (A) locally reduce the polarity of the maleimide compound; therefore, component (A) tends to exhibit excellent compatibility not only with highly polar compounds but also with low-polarity compounds. Thus, it is believed that the overall homogeneity of the cured product obtained from the resin composition of this embodiment is improved, thereby improving conductor adhesion.

[0050] Furthermore, the tensile modulus of elasticity (B) contained in the resin composition of this embodiment is 10 GPa or less at 25°C. It is believed that the resin that satisfies the tensile modulus of elasticity at 25°C has excellent compatibility with component (A) in terms of resin rigidity, molecular weight, polarity, etc., and can contribute to the improvement of dielectric properties, thus further improving the dielectric properties.

[0051] <(A)Component>

[0052] (A) The component is selected from one or more maleimide compounds and their derivatives, wherein the maleimide compound contains a fused ring of aromatic ring and aliphatic ring in its molecular structure and has two or more N-substituted maleimide groups.

[0053] (A) One ingredient may be used alone, or two or more ingredients may be used in combination.

[0054] From the viewpoint of dielectric properties and conductor adhesion, component (A) is preferably selected from one or more compounds selected from (i) and (ii) below.

[0055] (i) Maleimide compounds (a1) having a fused ring structure containing both aromatic and aliphatic rings in their molecular structure and having two or more N-substituted maleimide groups [hereinafter sometimes referred to as "maleimide compound (a1)" or "(a1) component"].

[0056] (ii) An aminomaleimide compound having structural units derived from maleimide compound (a1) and structural units derived from diamine compound (a2) [hereinafter sometimes referred to as "aminomaleimide compound (A1)" or "(A1) component"].

[0057] (maleimide compound (a1))

[0058] From the viewpoints of dielectric properties, conductor adhesion, and heat resistance, the preferred component (a1) is an aromatic maleimide compound having a fused ring structure containing both an aromatic and an aliphatic ring and having two or more N-substituted maleimide groups. Furthermore, the preferred component (a1) is an aromatic bismaleimide compound having a fused ring structure containing both an aromatic and an aliphatic ring and having two N-substituted maleimide groups.

[0059] It should be noted that, in this specification, "aromatic maleimide compound" refers to a compound having an N-substituted maleimide group directly bonded to the aromatic ring, and "aromatic bismaleimide compound" refers to a compound having two N-substituted maleimide groups directly bonded to the aromatic ring.

[0060] From the viewpoints of dielectric properties, conductor adhesion and ease of manufacture, the fused ring contained in component (a1) preferably has a fused bicyclic structure, and more preferably an indene ring.

[0061] As the (a1) component containing an indane ring, an aromatic bismaleimide compound containing an indane ring is preferred.

[0062] It should be noted that, in this specification, the indim ring refers to a fused bicyclic structure of an aromatic 6-membered ring and a saturated aliphatic 5-membered ring. At least one carbon atom in the cyclic carbon atom forming the indim ring has a bonding group for bonding with other groups constituting component (a1). The cyclic carbon atom having this bonding group and other cyclic carbon atoms may not have bonding groups, substituents, etc., but it is preferable to form a divalent group by having bonding groups other than those mentioned above.

[0063] In component (a1), the indane ring is preferably included as a divalent group as shown in the following general formula (a1-1).

[0064] [Chemical Formula 2]

[0065]

[0066] (where R is in the formula) a1 It is an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, where n1 is an integer from 0 to 3. R a2 ~R a4 Each is an alkyl group having 1 to 10 carbon atoms. * indicates a bonding site.

[0067] R in the above general formula (a1-1) a1 The alkyl groups shown have 1 to 10 carbon atoms, and examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. These alkyl groups can be either straight-chain or branched.

[0068] As R a1 The alkyl groups contained in the alkoxy groups with 1 to 10 carbon atoms and the alkylthio groups with 1 to 10 carbon atoms shown can be alkyl groups that are the same as the alkyl groups with 1 to 10 carbon atoms mentioned above.

[0069] As R a1 Aryl groups with 6 to 10 carbon atoms are shown, for example, phenyl and naphthyl.

[0070] As R a1 The aryl groups contained in the aryloxy groups with 6 to 10 carbon atoms and the arylthio groups with 6 to 10 carbon atoms shown can be aryl groups that are the same as the aryl groups with 6 to 10 carbon atoms mentioned above.

[0071] As R a1 Examples of cycloalkyl groups with 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0072] When n1 in the above general formula (a1-1) is an integer from 1 to 3, from the viewpoint of solvent solubility and reactivity, R a1 Preferably, it is 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, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0073] As R a2 ~R a4Alkyl groups with 1 to 10 carbon atoms are shown, and examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. These alkyl groups can be either straight-chain or branched. Wherein, R... a2 ~R a4 Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably methyl or ethyl, and even more preferably methyl.

[0074] In the above general formula (a1-1), n1 is an integer from 0 to 3. When n1 is 2 or 3, multiple R a1 They can be the same or different.

[0075] From the viewpoint of ease of manufacture, the divalent group represented by the above general formula (a1-1) is preferably n1 = 0 and R = 0. a2 ~R a4 It is a divalent group of methyl as shown in the following formula (a1-1').

[0076] [Chemical Formula 3]

[0077]

[0078] (In the formula, * indicates the bonding site.)

[0079] From the viewpoints of dielectric properties, conductor adhesion, heat resistance and ease of manufacture, the substance shown in the following general formula (a1-2) is preferred as the component (a1) containing the divalent group shown in the above general formula (a1-1).

[0080] [Chemical Formula 4]

[0081]

[0082] (where R is in the formula) a1 ~R a4 and n1 and R in the above general formula (a1-1) a1 ~R a4 Same as n1. R a5 Each of the following groups is independently an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an arylthio group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; n2 is independently an integer from 0 to 4; and n3 is a number from 0.95 to 10.0.

[0083] In the above general formula (a1-2), multiple R a1 Each other, multiple n1 each other, multiple R a5 Each n2 can be the same as or different from the others.

[0084] When n3 exceeds 1, multiple R a2 Each other, multiple R a3 Each other and multiple R a4 They can be the same or different.

[0085] R in the above general formula (a1-2) a5 The alkyl group represented has 1 to 10 carbon atoms, and examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. These alkyl groups can be either straight-chain or branched.

[0086] As R a5 The alkyl groups contained in the alkoxy groups with 1 to 10 carbon atoms and the alkylthio groups with 1 to 10 carbon atoms shown can be alkyl groups that are the same as the alkyl groups with 1 to 10 carbon atoms mentioned above.

[0087] As R a5 Aryl groups with 6 to 10 carbon atoms are shown, for example, phenyl and naphthyl.

[0088] As R a5 The aryl groups contained in the aryloxy groups with 6 to 10 carbon atoms and the arylthio groups with 6 to 10 carbon atoms shown can be aryl groups that are the same as the aryl groups with 6 to 10 carbon atoms mentioned above.

[0089] As R a5 Examples of cycloalkyl groups with 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0090] From the perspective of solvent solubility and ease of manufacture, R a5 Preferably, the alkyl group has 1 to 4 carbon atoms, the cycloalkyl group has 3 to 6 carbon atoms, and the aryl group has 6 to 10 carbon atoms; more preferably, the alkyl group has 1 to 3 carbon atoms; and even more preferably, the methyl group has 1 to 3 carbon atoms.

[0091] In the above general formula (a1-2), n2 is an integer from 0 to 4. From the viewpoint of compatibility with other resins, dielectric properties, conductor adhesion and ease of manufacture, it is preferably an integer from 0 to 3, and more preferably 0 or 2.

[0092] It should be noted that by making n2 ≥ 1, the benzene ring and the N-substituted maleimide group have a distorted conformation, which tends to further improve solvent solubility by suppressing intermolecular stacking. From the viewpoint of suppressing intermolecular stacking, when n2 ≥ 1, R a5 The substitution position is preferably ortho relative to the N-substituted maleimide group.

[0093] From the viewpoints of dielectric properties, conductor adhesion, solvent solubility, processability, and heat resistance, n3 in the above general formula (a1-2) is preferably a value of 0.98 to 8.0, more preferably a value of 1.0 to 7.0, and even more preferably a value of 1.1 to 6.0. It should be noted that n3 represents the average number of structural units containing indene rings.

[0094] From the viewpoints of dielectric properties, conductor adhesion, solvent solubility and ease of manufacture, the component (a1) shown in the above general formula (a1-2) is more preferably the substance shown in the following general formula (a1-3) or the substance shown in the following general formula (a1-4).

[0095] [Chemical Formula 5]

[0096]

[0097] (where R is in the formula) a1 ~R a5 n1 and n3 are related to R in the above general formula (a1-2). a1 ~R a5 (n1 and n3 are the same.)

[0098] [Chemical Formula 6]

[0099]

[0100] (where R is in the formula) a1 ~R a4 n1 and n3 are related to R in the above general formula (a1-2). a1 ~R a4 (n1 and n3 are the same.)

[0101] Examples of compounds that can be represented as component (a1) in the above general formula (a1-3) include compounds represented by the following general formula (a1-3-1), compounds represented by the following general formula (a1-3-2), and compounds represented by the following general formula (a1-3-3).

[0102] [Chemical Formula 7]

[0103]

[0104] (In the formula, n3 is the same as n3 in the above general formula (a1-2).)

[0105] Examples of compounds represented by the above general formula (a1-4) include compounds represented by the following general formula (a1-4-1).

[0106] [Chemical Formula 8]

[0107]

[0108] (In the formula, n3 is the same as n3 in the above general formula (a1-2).)

[0109] (a1) The number average molecular weight of the component is not particularly limited, but from the viewpoint of compatibility with other resins, conductor adhesion and heat resistance, it is preferably 600 to 3,000, more preferably 800 to 2,000, and even more preferably 1,000 to 1,500.

[0110] (a1) The component can be produced, for example, by reacting an intermediate amine compound (hereinafter sometimes simply referred to as "intermediate amine compound") containing a fused ring of aromatic and aliphatic rings with maleic anhydride (hereinafter sometimes referred to as "maleimide reaction").

[0111] The following describes the manufacturing method of component (a1) using a maleimide compound containing an indanthione ring as both an aromatic and aliphatic fused ring as an example.

[0112] An intermediate amine compound containing an indenyl ring, such as a maleimide compound, can be obtained, for example, by reacting a compound of the following general formula (a1-5) [hereinafter, sometimes referred to as "compound A"] with a compound of the following general formula (a1-6) [hereinafter, sometimes referred to as "compound B"] in the presence of an acid catalyst [hereinafter, sometimes referred to as a "cyclization reaction"].

[0113] [Chemical Formula 9]

[0114]

[0115] (where R is in the formula) a1 and n1 and R in the above general formula (a1-1) a1 Same as n1. R a6 Each is independently a group represented by formula (a1-5-1) or formula (a1-5-2) above, with 2 R a6 At least one R in a6 The adjacent position is a hydrogen atom.

[0116] [Chemical Formula 10]

[0117]

[0118] (where R is in the formula) a5 and n2 and R in the above general formula (a1-2) a5 Same as n2. (In this case, at least one of the ortho and para positions of the amino group is a hydrogen atom.)

[0119] [Chemical Formula 11]

[0120]

[0121] (where R is in the formula) a1 R a5 and n1~n3 and R in the above general formula (a1-2) a1 R a5 Same as n1 to n3.

[0122] Examples of compound A include, for example, p-diisopropenylbenzene or m-diisopropenylbenzene, p-bis(α-hydroxyisopropyl)benzene or m-bis(α-hydroxyisopropyl)benzene, 1-(α-hydroxyisopropyl)-3-isopropenylbenzene, 1-(α-hydroxyisopropyl)-4-isopropenylbenzene, mixtures thereof, nucleoalkyl-substituted derivatives of these compounds, nucleohalogen-substituted derivatives of these compounds, etc.

[0123] Examples of the aforementioned nucleoalkyl substituents include diisopropenyltoluene and bis(α-hydroxyisopropyl)toluene.

[0124] Examples of the aforementioned nucleohalogen substitutes include dichloroisopropenylbenzene and chlorobis(α-hydroxyisopropyl)benzene.

[0125] These compounds A can be used alone or in combination of two or more.

[0126] Examples of compound B include: aniline, dimethylaniline, diethylaniline, diisopropylaniline, ethylmethylaniline, cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, chloroaniline, dichloroaniline, toluidine, dimethylaniline, phenylaniline, nitroaniline, aminophenol, methoxyaniline, ethoxyaniline, phenoxyaniline, naphthioaniline, aminothiol, methylthioaniline, ethylthioaniline, phenylthioaniline, etc. These compounds B can be used alone or in combination of two or more.

[0127] Regarding the cyclization reaction, for example, compound A and compound B are added at a molar ratio (compound B / compound A) preferably 0.1 to 2.0, more preferably 0.15 to 1.5, and even more preferably 0.2 to 1.0 to carry out the first stage reaction.

[0128] Next, preferably, the additional compound B is added at a ratio of 0.5 to 20, more preferably 0.6 to 10, and even more preferably 0.7 to 5 relative to the previously added compound A (additional compound B / compound A), to carry out the second stage reaction.

[0129] Examples of acid catalysts used in cyclization reactions include: inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica-alumina, zeolite, and strongly acidic ion exchange resins; and heteropolyhydrochloric acid. One type can be used alone, or two or more can be used in combination.

[0130] From the viewpoint of reaction rate and reaction uniformity, the amount of acid catalyst is preferably 5 to 40 parts by mass relative to the total amount of initially added compound A and compound B (100 parts by mass), more preferably 5 to 35 parts by mass, and even more preferably 5 to 30 parts by mass.

[0131] From the viewpoint of reaction rate and reaction uniformity, the reaction temperature of the cyclization reaction is preferably 100-300°C, more preferably 130-250°C, and even more preferably 150-230°C.

[0132] From the viewpoint of productivity and full reaction, the reaction time of the cyclization reaction is preferably 2 to 24 hours, more preferably 4 to 16 hours, and even more preferably 8 to 12 hours.

[0133] These reaction conditions can be adjusted appropriately according to the type of raw materials used, and there are no particular limitations.

[0134] It should be noted that solvents such as toluene, xylene, and chlorobenzene can be used in cyclization reactions as needed. Additionally, if water is produced as a byproduct during cyclization, the dehydration reaction can be promoted by using a solvent capable of azeotropic dehydration.

[0135] Next, the intermediate amine compound obtained above is reacted with maleic anhydride in an organic solvent to carry out a maleimide reaction, thereby converting the primary amino group of the intermediate amine compound into a maleimide group. By carrying out this maleimide reaction, component (a1) can be obtained.

[0136] The equivalence ratio (maleic anhydride / primary amine) of maleic anhydride to the primary amine compound in the maleimide reaction is not particularly limited, but from the viewpoint of reducing the amount of unreacted primary amine and unreacted maleic anhydride, it is preferably 1.0 to 1.5, more preferably 1.05 to 1.3, and even more preferably 1.1 to 1.2.

[0137] The amount of organic solvent used in the maleimide reaction is not particularly limited. From the viewpoint of reaction rate and reaction uniformity, it is preferably 50 to 5,000 parts by mass relative to the total amount of intermediate amine compound and maleic anhydride of 100 parts by mass, more preferably 70 to 2,000 parts by mass, and even more preferably 100 to 500 parts by mass.

[0138] The maleimide reaction is preferably carried out in two stages with the intermediate amine compound and maleic anhydride.

[0139] The reaction temperature in the first stage is preferably 10–100°C, more preferably 20–70°C, and even more preferably 30–50°C.

[0140] The reaction time in the first stage is preferably 0.5 to 12 hours, more preferably 0.7 to 8 hours, and even more preferably 1 to 4 hours.

[0141] The second stage reaction is preferably carried out after the first stage reaction is completed, following the addition of a catalyst such as toluenesulfonic acid.

[0142] The reaction temperature in the second stage is preferably 90–130°C, more preferably 100–125°C, and even more preferably 105–120°C.

[0143] The reaction time in the second stage is preferably 2 to 24 hours, more preferably 4 to 15 hours, and even more preferably 6 to 10 hours.

[0144] The reaction conditions described above can be adjusted appropriately based on the type of raw materials used, and there are no particular limitations.

[0145] After the reaction, unreacted raw materials and other impurities can be removed by purification methods such as water washing, as needed.

[0146] The (a1) component obtained by the above method sometimes contains maleimide compounds that do not contain an indane ring as byproducts. For example, a maleimide compound that does not contain an indane ring is a compound in the above general formula (a1-2) where n3 is 0.

[0147] The content of maleimide compounds without an indane ring, which are byproducts in the reaction products, can be determined, for example, by measuring the GPC of the reaction products. Specifically, for example, calibration curves can be prepared using compounds with n3 values ​​of 0 to 4 in the above general formula (a1-2) to show the elution time relative to the number of n3. Based on this, the number of n3 and its average value of the compounds contained in the reaction products can be determined from the elution times of the peaks observed in the GPC chromatogram of the reaction products. Furthermore, the proportion of compounds with the n3 number represented by each peak can be determined from the area ratio of each peak.

[0148] (a1) The preferred component is a substance with a low content of maleimide compounds that do not contain an indane ring, which are byproducts. Therefore, in the GPC chromatogram of the above reaction products, the area ratio of the peak area of ​​maleimide compounds that do not contain an indane ring, which are byproducts, to the total peak area of ​​the reaction products is preferably 40% or less, more preferably 30% or less, even more preferably 20% or less, and particularly preferably 10% or less.

[0149] (Aminomaleimide compound (A1))

[0150] The aminomaleimide compound (A1) is an aminomaleimide compound having structural units derived from maleimide compound (a1) and structural units derived from diamine compound (a2). It should be noted that component (A1) is equivalent to a derivative of maleimide compound (a1).

[0151] (A1) Components can be used alone or in combination of two or more.

[0152] [Structural units derived from maleimide compound (a1)]

[0153] As a structural unit derived from component (a1), for example, at least one of the N-substituted maleimide groups in component (a1) undergoes a Michael addition reaction with an amino group in diamine compound (a2) to form a structural unit.

[0154] The structural units derived from component (a1) contained in component (A1) can be a single type or two or more types.

[0155] The content of structural units derived from component (a1) in the aminomaleimide compound (A1) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and even more preferably 60 to 90% by mass. If the content of structural units derived from component (a1) in component (A1) is within the above range, there is a tendency for the dielectric properties and film processability to become better.

[0156] [Derived from the structural unit of the diamine compound (a2)]

[0157] As a structural unit derived from component (a2), for example, one or both of the two amino groups of component (a2) undergo a Michael addition reaction with the N-substituted maleimide group of maleimide compound (a1).

[0158] The structural units derived from component (a2) contained in component (A1) can be a single type or two or more types.

[0159] (a2) The amino group of the component is preferably a primary amino group.

[0160] Examples of structural units derived from diamine compounds (a2) having two primary amino groups include groups represented by the following general formula (a2-1) and groups represented by the following general formula (a2-2).

[0161] [Chemical Formula 12]

[0162]

[0163] (where X) a1 (This is a divalent organic group; * indicates a bonding position with other structures.)

[0164] In the above general formulas (a2-1) and (a2-2), X a1 It is a divalent organic group, which is equivalent to the divalent group obtained by removing two amino groups from component (a2).

[0165] In the above general formulas (a2-1) and (a2-2), X a1 Preferably, it is a divalent group as shown in the following general formula (a2-3).

[0166] [Chemical Formula 13]

[0167]

[0168] (where R is in the formula) a11 and R a12 Each is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. X a2 It is an alkylene group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyl group, a ketone group, a fluorene group, a single bond, or a divalent group as shown in the following general formulas (a2-3-1) or (a2-3-2). p1 and p2 are each independently integers from 0 to 4. * indicates the bonding site.

[0169] [Chemical Formula 14]

[0170]

[0171] (where R is in the formula) a13 and R a14 Each is independently an aliphatic hydrocarbon group or halogen atom with 1 to 5 carbon atoms. X a3 Alkyl groups with 1 to 5 carbon atoms, alkylidene groups with 2 to 5 carbon atoms, m-phenylene diisopropylidene, p-phenylene diisopropylidene, ether groups, thioether groups, sulfonyl groups, carbonyl groups, ketone groups, or single bonds. p3 and p4 are each independent integers from 0 to 4. * indicates the bonding site.

[0172] [Chemical Formula 15]

[0173]

[0174] (where R is in the formula) a15 It consists of an aliphatic hydrocarbon group or a halogen atom with 1 to 5 carbon atoms. X a4 and X a5 Each group can be an alkyl group (1-5 carbon atoms), an alkylidene group (2-5 carbon atoms), an ether group, a thioether group, a sulfonyl group, a carbonyl group, a ketone group, or a single bond. p5 is an integer from 0 to 4. * indicates the bonding site.

[0175] R in the above general formulas (a2-3), (a2-3-1), and (a2-3-2) a11 R a12 R a13 R a14 and R a15 Examples of aliphatic hydrocarbon groups with 1 to 5 carbon atoms include alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; and alkenyl and alkynyl groups with 2 to 5 carbon atoms. The aliphatic hydrocarbon group with 1 to 5 carbon atoms can be either straight-chain or branched. Preferably, the aliphatic hydrocarbon group with 1 to 3 carbon atoms is used, more preferably an alkyl group with 1 to 3 carbon atoms, and even more preferably methyl or ethyl.

[0176] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0177] X in the above general formula (a2-3) a2 X in the above general formula (a2-3-1) a3 And X in the above general formula (a2-3-2) a4 and X a5 Examples of alkyl groups with 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentaneene. Among these alkyl groups with 1 to 5 carbon atoms, those with 1 to 3 carbon atoms are preferred, those with 1 or 2 carbon atoms are more preferred, and methylene is even more preferred.

[0178] X in the above general formula (a2-3) a2 X in the above general formula (a2-3-1) a3 and X in the above general formula (a2-3-2) a4 and X a5Examples of alkylidene groups with 2 to 5 carbon atoms include ethoxyl, propionyl, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene. Among these alkylidene groups with 2 to 5 carbon atoms, those with 2 to 4 carbon atoms are preferred, those with 2 or 3 carbon atoms are more preferred, and isopropylidene is even more preferred.

[0179] In the above general formula (a2-3), p1 and p2 are each an integer from 0 to 4. From the viewpoint of ease of obtaining, they are preferably integers from 0 to 3, more preferably integers from 0 to 2, and even more preferably 0 or 2.

[0180] When p1 or p2 is an integer greater than 2, multiple R a11 R to each other or multiple R a12 They can be the same or different.

[0181] In the above general formula (a2-3-1), p3 and p4 are each an integer from 0 to 4. From the viewpoint of ease of obtaining, they are preferably integers from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0182] When p3 or p4 is an integer greater than 2, multiple R a13 R to each other or multiple R a14 They can be the same or different.

[0183] In the above general formula (a2-3-2), p5 is an integer from 0 to 4. From the viewpoint of ease of obtaining, it is preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0184] When p5 is an integer greater than 2, multiple R a15 They can be the same or different.

[0185] The content of structural units derived from component (a2) in the aminomaleimide compound (A1) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and even more preferably 10 to 40% by mass. If the content of structural units derived from component (a2) in the aminomaleimide compound (A1) is within the above range, there is a tendency for the dielectric properties, heat resistance, flame retardancy, and glass transition temperature to become better.

[0186] Examples of components (a2) include: 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)] [Phenylacetyl]propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 4,4'-[1,3-phenylenebis(1-methylethoxy)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethoxy)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethoxy)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene, etc.

[0187] Of which, as component (a2), from the viewpoint of excellent solubility in organic solvents, reactivity with maleimide compound (a1), and heat resistance, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethoxy)]bisaniline, and 4,4'-[1,4-phenylenebis(1-methylethoxy)]bisaniline are preferred. Furthermore, from the viewpoint of excellent dielectric properties and low water absorption, component (a2) is preferably 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane. Furthermore, from the viewpoint of excellent mechanical properties such as high adhesion to conductors, elongation, and tensile strength, component (a2) is preferably 2,2-bis[4-(4-aminophenoxy)phenyl]propane. Moreover, from the viewpoint of excellent solubility in organic solvents, reactivity during synthesis, heat resistance, high adhesion to conductors, dielectric properties, and low hygroscopicity, component (a2) is preferably 4,4'-[1,3-phenylenebis(1-methylethoxy)]bisaniline or 4,4'-[1,4-phenylenebis(1-methylethoxy)]bisaniline.

[0188] In the aminomaleimide compound (A1), the equivalence ratio (Ta2 / Ta1) of the total equivalent amount (Ta2) of the -NH2 group (including -NH2) from the diamine compound (a2) to the total equivalent amount (Ta1) of the N-substituted maleimide group from the maleimide compound (a1) is not particularly limited, but from the viewpoint of dielectric properties, heat resistance, flame retardancy and glass transition temperature, it is preferably 0.05 to 10, more preferably 0.5 to 7, and even more preferably 1 to 5. It should be noted that the N-substituted maleimide group from the maleimide compound (a1) also includes the N-substituted maleimide itself.

[0189] The number-average molecular weight of the aminomaleimide compound (A1) is not particularly limited, but from the viewpoint of processability and formability, it is preferably 400 to 10,000, more preferably 500 to 5,000, and even more preferably 600 to 2,000.

[0190] (Method for manufacturing aminomaleimide compound (A1))

[0191] Component (A1) can be manufactured, for example, by reacting a maleimide compound (a1) with a diamine compound (a2) in an organic solvent.

[0192] By reacting maleimide compound (a1) with diamine compound (a2), an aminomaleimide compound (A1) can be obtained by Michael addition reaction of maleimide compound (a1) and diamine compound (a2).

[0193] When reacting maleimide compound (a1) with diamine compound (a2), a reaction catalyst may be used as needed.

[0194] Examples of reaction catalysts include: acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazolium and phenylimidazolium; and phosphorus-based catalysts such as triphenylphosphine. They can be used individually or in combination of two or more.

[0195] The amount of reaction catalyst is not particularly limited. From the viewpoint of reaction rate and reaction uniformity, it is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the combined amount of maleimide compound (a1) and diamine compound (a2), more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass.

[0196] From the viewpoints of workability such as reaction rate and inhibition of gelation of products in the reaction, the reaction temperature of Michael addition reaction is preferably 50-160°C, more preferably 60-150°C, and even more preferably 70-140°C.

[0197] From the viewpoint of productivity and full reaction, the reaction time of the Michael addition reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and even more preferably 2 to 6 hours.

[0198] These reaction conditions can be adjusted appropriately according to the type of raw materials used, and there are no particular limitations.

[0199] By adding or concentrating an organic solvent in the Michael addition reaction, the solids concentration and viscosity of the reaction solution can be adjusted. The solids concentration of the reaction solution is not particularly limited, but is preferably 10–90% by mass, more preferably 15–85% by mass, and even more preferably 20–80% by mass. If the solids concentration of the reactants is above the lower limit mentioned above, a good reaction rate and improved productivity tend to be obtained. Furthermore, if the solids concentration of the reactants is below the upper limit mentioned above, better solubility, improved stirring efficiency, and a tendency to further suppress gelation of the products in the reaction tend to be obtained.

[0200] <(B) Component>

[0201] The resin composition of this embodiment contains a resin with a tensile modulus of elasticity of 10 GPa or less at 25°C as component (B), thereby achieving excellent dielectric properties and conductor adhesion.

[0202] It should be noted that in the resin composition of this embodiment, the resin equivalent to component (A) is not included in component (B).

[0203] (B) Components can be used alone or in combination of two or more.

[0204] In this specification, the tensile modulus of elasticity at 25°C is a value determined by the following method.

[0205] (Method for determining tensile modulus of elasticity at 25℃)

[0206] A test piece with a width of 10 mm, a length of 80 mm, and a thickness of 0.2 mm was prepared from the resin to be tested. The test piece was clamped at both ends along its long side using upper and lower clamps spaced 60 mm apart. Next, using a tensile testing machine at a room temperature of 25°C and a tensile speed of 5 mm / min, the tensile modulus of elasticity at 25°C was obtained. It should be noted that the tensile modulus of elasticity was calculated according to the international standard ISO 5271 (1993).

[0207] Here, the "resin with a tensile modulus of elasticity of 10 GPa or less at 25°C" in this embodiment includes: a resin that cannot be used to make the above-mentioned test piece due to its low tensile modulus of elasticity at 25°C; and a resin that, for the same reason, cannot be used to perform a tensile test under the above conditions even if the above-mentioned test piece can be made.

[0208] The tensile modulus of elasticity of component (B) at 25°C is 10 GPa or less, preferably 7 GPa or less, more preferably 5 GPa or less, even more preferably 3 GPa or less, even more preferably 2 GPa or less, particularly preferably 1 GPa or less, and most preferably 0.6 GPa or less. If the tensile modulus of elasticity of component (B) at 25°C is below the above-mentioned upper limit, the resulting resin composition tends to have excellent dielectric properties and conductor adhesion.

[0209] The tensile modulus of elasticity at 25°C of component (B) is not particularly limited, but is preferably 0.005 GPa or more, more preferably 0.01 GPa or more, and even more preferably 0.03 GPa or more. If the tensile modulus of elasticity at 25°C of component (B) is above the above lower limit, there is a tendency to maintain the heat resistance, etc., of the obtained resin composition well.

[0210] The number-average molecular weight of component (B) is not particularly limited, but is preferably 400 to 500,000, more preferably 600 to 350,000, and even more preferably 700 to 200,000. If the number-average molecular weight of component (B) is above the lower limit mentioned above, there is a tendency to maintain the heat resistance, etc., of the obtained resin composition well. In addition, if the number-average molecular weight of component (B) is below the upper limit mentioned above, there is a tendency to have excellent dielectric properties and conductor adhesion of the obtained resin composition.

[0211] As a component (B), thermoplastic resins and their modifications are preferred examples.

[0212] It should be noted that component (B) can be a thermosetting resin, and preferably, component (B) whose cured product is an elastomer. It should also be noted that "elastomer" here refers to a polymer with a glass transition temperature of 25°C or less, as determined by differential scanning calorimetry according to JIS K 6240:2011.

[0213] Examples of components (B) include polyolefin resins, polyphenylene ether resins, silicone resins, epoxy resins, polyurethane resins, polyester resins, polyamide resins, and polyacrylic resins.

[0214] From the viewpoint of compatibility, dielectric properties and conductor adhesion with component (A), component (B) preferably contains one or more selected from polyolefin resins, polyphenylene ether resins, silicone resins and epoxy resins, more preferably contains one or more selected from polyolefin resins and polyphenylene ether resins, and even more preferably contains a polyolefin resin.

[0215] (Polyolefin resins)

[0216] As a polyolefin resin, there are no special restrictions as long as the tensile modulus of elasticity at 25°C is below 10 GPa.

[0217] As a polyolefin resin, it can be used alone or in combination with two or more types.

[0218] Examples of polyolefin resins include homopolymers or copolymers of monoolefins and dienes, and their modified forms.

[0219] Examples of monoolefins include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and styrene.

[0220] Examples of dienes include non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethyl norbornene; and conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene.

[0221] From the viewpoint of compatibility with other resins, dielectric properties, and conductive adhesion, conjugated diene polymer (B1) [hereinafter sometimes referred to as "(B1) component"], modified conjugated diene polymer (B2) [hereinafter sometimes referred to as "(B2) component"], and styrene elastomer (B3) [hereinafter sometimes referred to as "(B3) component"] are preferred as polyolefin resins.

[0222] [Conjugated diene polymer (B1)]

[0223] (B1) Component can be a polymer of one conjugated diene compound or a polymer of two or more conjugated diene compounds.

[0224] In addition, component (B1) can be a substance formed by copolymerizing one or more conjugated diene compounds with one or more monomers other than conjugated diene compounds.

[0225] When component (B1) is a copolymer, there is no particular limitation on the polymerization method; it can be any of random polymerization, block polymerization, or graft polymerization.

[0226] (B1) Components can be used alone or in combination of two or more.

[0227] As component (B1), from the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion, a conjugated diene polymer having vinyl groups in the side chain is preferred, and a conjugated diene polymer having multiple vinyl groups in the side chain is more preferred.

[0228] The number of vinyl groups in one molecule of component (B1) is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties and conductor adhesion, it is preferable to have 3 or more, more preferably 5 or more, and even more preferably 10 or more. The upper limit of the number of vinyl groups in one molecule of component (B1) is not particularly limited, and it can be 100 or less, 80 or less, or 60 or less.

[0229] Examples of component (B1) include, for instance, 1,2-vinyl polybutadiene, 1,2-vinyl butadiene-styrene copolymer, and 1,2-vinyl polyisoprene. From the viewpoint of dielectric properties and heat resistance, 1,2-vinyl polybutadiene and 1,2-vinyl butadiene-styrene copolymer are preferred, and 1,2-vinyl polybutadiene is more preferred. Furthermore, as 1,2-vinyl polybutadiene, a 1,2-vinyl polybutadiene homopolymer is preferred.

[0230] The 1,2-vinyl group in component (B1) refers to the vinyl group contained in the structural unit of butadiene as shown in formula (B1-1).

[0231] [Chemical Formula 16]

[0232]

[0233] When component (B1) is polybutadiene having 1,2-vinyl groups, the content of the 1,2-vinyl structural units [hereinafter sometimes referred to as "vinyl content"] relative to all structural units derived from butadiene constituting the polybutadiene is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, conductor adhesion, and heat resistance, it is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 85 mol% or more. Furthermore, there is no particular upper limit to the vinyl content; it can be 100 mol% or less, 95 mol% or less, or even 90 mol% or less. As the 1,2-vinyl structural units, structural units derived from butadiene shown in formula (B1-1) above are preferred.

[0234] From the same point of view, polybutadiene having 1,2-vinyl groups is preferably 1,2-polybutadiene homopolymers.

[0235] The tensile modulus of elasticity at 25°C of component (B1) is preferably 0.005 to 0.5 GPa, more preferably 0.01 to 0.3 GPa, and even more preferably 0.03 to 0.1 GPa, from the viewpoint of further improving the dielectric properties and conductor adhesion of the obtained resin composition and maintaining good heat resistance, as described in the preferred range of the tensile modulus of elasticity at 25°C of component (B1) above.

[0236] The number average molecular weight of component (B1) is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, conductor adhesion and heat resistance, it is preferably 400 to 3,000, more preferably 600 to 2,000, and even more preferably 800 to 1,500.

[0237] [Modified conjugated diene polymer (B2)]

[0238] (B) Component preferably contains a modified conjugated diene polymer (B2) as a polyolefin resin. From the viewpoint of compatibility with other resins, dielectric properties, and conductor adhesion, it is more preferable to contain a modified conjugated diene polymer as a polyolefin resin, which is obtained by modifying a conjugated diene polymer (b1) having vinyl groups on its side chains [hereinafter, sometimes referred to as "(b1) component"]. with a maleimide compound (b2) having two or more N-substituted maleimide groups [hereinafter, sometimes referred to as "(b2) component".].

[0239] (B2) Components can be used alone or in combination of two or more.

[0240] As component (b1), a conjugated diene polymer having vinyl groups in the side chain, as described above as component (B1), can be used, and the same is preferred.

[0241] (b1) One ingredient may be used alone, or two or more ingredients may be used in combination.

[0242] (b2) There are no particular restrictions on the composition as long as it is a maleimide compound having two or more N-substituted maleimide groups.

[0243] (b2) One ingredient may be used alone, or two or more ingredients may be used in combination.

[0244] As component (b2), from the viewpoint of compatibility with other resins, dielectric properties, and conductor adhesion, it is preferably a maleimide compound described as the maleimide compound (a1) above, which contains a fused ring of aromatic and aliphatic rings in its molecular structure and has two or more N-substituted maleimide groups. The preferred embodiment of this maleimide compound is the same as the preferred embodiment of the maleimide compound (a1) described above.

[0245] (b2) Component (a1) may be a maleimide compound other than maleimide compound (a1) [hereinafter, sometimes referred to as "(b2i) component"].

[0246] As the (b2i) component, the maleimide compound represented by the following general formula (b2-1) is preferred.

[0247] [Chemical Formula 17]

[0248]

[0249] (where X) b1 (A divalent organic group consisting of a fused ring that does not contain aromatic or aliphatic rings.)

[0250] In the above general formula (b2-1), X b1 It is a divalent organic group that is a fused ring without aromatic or aliphatic rings, equivalent to the divalent group obtained by removing two N-substituted maleimide groups from the (b2i) component.

[0251] X in the above general formula (b2-1) b1 Examples of divalent organic groups represented include: divalent groups represented by the following general formula (b2-2), divalent groups represented by the following general formula (b2-3), divalent groups represented by the following general formula (b2-4), divalent groups represented by the following general formula (b2-5), divalent groups represented by the following general formula (b2-6), etc.

[0252] [Chemical Formula 18]

[0253]

[0254] (where R is in the formula) b1 It consists of an aliphatic hydrocarbon group or a halogen atom with 1 to 5 carbon atoms. q1 is an integer from 0 to 4. * indicates a bonding site.

[0255] R in the above general formula (b2-2) b1 Examples of aliphatic hydrocarbon groups with 1 to 5 carbon atoms include alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; and alkenyl and alkynyl groups with 2 to 5 carbon atoms. The aliphatic hydrocarbon group with 1 to 5 carbon atoms can be either straight-chain or branched. Preferably, the aliphatic hydrocarbon group with 1 to 3 carbon atoms is used, more preferably an alkyl group with 1 to 3 carbon atoms, and even more preferably methyl.

[0256] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0257] In the above general formula (b2-2), q1 is an integer from 0 to 4. From the viewpoint of ease of obtaining, it is preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0258] When q1 is an integer greater than 2, multiple R b1 They can be the same or different.

[0259] [Chemical Formula 19]

[0260]

[0261] (where R is in the formula) b2 and R b3Each is independently an aliphatic hydrocarbon group or halogen atom with 1 to 5 carbon atoms. X b2 It is an alkyl group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyl group, a ketone group, a single bond, or a divalent group as shown in the following general formula (b2-3-1). q2 and q3 are each independently integers from 0 to 4.

[0262] * indicates the bonding site.

[0263] R in the above general formula (b2-3) b2 and R b3 Examples of aliphatic hydrocarbon groups with 1 to 5 carbon atoms include alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; and alkenyl and alkynyl groups with 2 to 5 carbon atoms. The aliphatic hydrocarbon group with 1 to 5 carbon atoms can be either linear or branched. From the viewpoint of compatibility with other resins and inhibiting gelation of products in the reaction, aliphatic hydrocarbon groups with 1 to 3 carbon atoms are preferred, alkyl groups with 1 to 3 carbon atoms are more preferred, and methyl and ethyl groups are even more preferred.

[0264] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0265] As X in the above general formula (b2-3) b2 Examples of alkyl groups with 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentaneene. Among these alkyl groups with 1 to 5 carbon atoms, those with 1 to 3 carbon atoms are preferred, those with 1 or 2 carbon atoms are more preferred, and methylene is even more preferred.

[0266] As X in the above general formula (b2-3) b2 Examples of alkylidene groups with 2 to 5 carbon atoms include ethoxylide, propionyl, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene. Among these, alkylidene groups with 2 to 4 carbon atoms are preferred, alkylidene groups with 2 or 3 carbon atoms are more preferred, and isopropylidene groups are even more preferred.

[0267] In the above general formula (b2-3), q2 and q3 are each independently an integer from 0 to 4. From the viewpoint of ease of acquisition, compatibility with other resins and inhibition of gelation of products in the reaction, they are preferably integers from 1 to 3, more preferably 1 or 2, and even more preferably 2.

[0268] From the viewpoints of ease of acquisition, compatibility with other resins, and inhibition of gelation of products in the reaction, q2+q3 is preferably an integer from 1 to 8, more preferably an integer from 2 to 6, and even more preferably 4.

[0269] In the case where q2 or q3 is an integer greater than 2, multiple R b2 R to each other or multiple R b3 They can be the same or different.

[0270] In the above general formula (b2-3), X b2 The divalent groups represented by the general formula (b2-3-1) are as follows.

[0271] [Chemical Formula 20]

[0272]

[0273] (where R is in the formula) b4 and R b5 Each is independently an aliphatic hydrocarbon group or halogen atom with 1 to 5 carbon atoms. X b3 It can be an alkyl group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyl group, a ketone group, or a single bond. q4 and q5 are each independent integers from 0 to 4. * indicates the bonding site.

[0274] R in the above general formula (b2-3-1) b4 and R b5 Examples of aliphatic hydrocarbon groups with 1 to 5 carbon atoms include alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; and alkenyl and alkynyl groups with 2 to 5 carbon atoms. The aliphatic hydrocarbon group with 1 to 5 carbon atoms can be either straight-chain or branched. Preferably, the aliphatic hydrocarbon group with 1 to 3 carbon atoms is used, more preferably an alkyl group with 1 to 3 carbon atoms, and even more preferably methyl.

[0275] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0276] As X in the above general formula (b2-3-1) b3 Examples of alkyl groups with 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentaneene. Among these alkyl groups with 1 to 5 carbon atoms, those with 1 to 3 carbon atoms are preferred, those with 1 or 2 carbon atoms are more preferred, and methylene is even more preferred.

[0277] As X in the above general formula (b2-3-1) b3Examples of alkylidene groups with 2 to 5 carbon atoms include ethoxylide, propionyl, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene. Among these, alkylidene groups with 2 to 4 carbon atoms are preferred, alkylidene groups with 2 or 3 carbon atoms are more preferred, and isopropylidene groups are even more preferred.

[0278] As X in the above general formula (b2-3-1) b3 In the above selection, alkylidene groups with 2 to 5 carbon atoms are preferred, alkylidene groups with 2 to 4 carbon atoms are more preferred, and isopropylidene groups are even more preferred.

[0279] In the above general formula (b2-3-1), q4 and q5 are each an integer from 0 to 4. From the viewpoint of ease of acquisition, they are preferably integers from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0280] In the case where q4 or q5 is an integer greater than 2, multiple R b4 R to each other or multiple R b5 They can be the same or different.

[0281] As X in the above general formula (b2-3) b2 In the above selection, alkyl groups with 1 to 5 carbon atoms, alkylidene groups with 2 to 5 carbon atoms, and divalent groups represented by the above general formula (b2-3-1) are preferred, alkyl groups with 1 to 5 carbon atoms are more preferred, and methylene groups are even more preferred.

[0282] [Chemical Formula 21]

[0283]

[0284] (In the formula, q6 is an integer from 0 to 10. * indicates the bonding site.)

[0285] In the above general formula (b2-4), from the viewpoint of ease of obtaining, q6 is preferably an integer from 0 to 5, more preferably an integer from 0 to 4, and even more preferably an integer from 0 to 3.

[0286] [Chemical Formula 22]

[0287]

[0288] (In the formula, q7 is a number from 0 to 5. * indicates the bonding site.)

[0289] [Chemical Formula 23]

[0290]

[0291] (where R is in the formula) b6 and R b7Each group consists independently of a hydrogen atom or an aliphatic hydrocarbon group with 1 to 5 carbon atoms. q8 is an integer from 1 to 8. * indicates a bonding site.

[0292] R in the above general formula (b2-6) b6 and R b7 The aliphatic hydrocarbon groups representing 1 to 5 carbon atoms include, for example, alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; alkenyl groups with 2 to 5 carbon atoms; and alkynyl groups with 2 to 5 carbon atoms. The aliphatic hydrocarbon groups with 1 to 5 carbon atoms can be either straight-chain or branched.

[0293] In the above general formula (b2-6), q8 is an integer from 1 to 8, preferably an integer from 1 to 5, more preferably an integer from 1 to 3, and even more preferably 1. When q8 is an integer of 2 or more, multiple R... b6 R to each other or multiple R b7 They can be the same or different.

[0294] Examples of (b2i) components include: aromatic bismaleimide compounds having two N-substituted maleimide groups bonded to an aromatic ring; aromatic polymaleimide compounds having three or more N-substituted maleimide groups bonded to an aromatic ring; and aliphatic maleimide compounds having N-substituted maleimide groups bonded to an aliphatic group.

[0295] Specific examples of (b2i) components include: N,N'-ethylidene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidephenyl)methane, bis(3-methyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(4-maleimidephenyl) ether, bis(4-maleimidephenyl) sulfone, bis(4-maleimidephenyl) sulfide, bis(4-maleimidephenyl) thioether, bis (4-maleimide phenyl) ketone, bis(4-maleimide cyclohexyl)methane, 1,4-bis(4-maleimide phenyl)cyclohexane, 1,4-bis(maleimide methyl)cyclohexane, 1,4-bis(maleimide methyl)benzene, 1,3-bis(4-maleimide phenoxy)benzene, 1,3-bis(3-maleimide phenoxy)benzene, bis[4-(3-maleimide phenoxy)phenyl]methane, bis[4-(4-maleimide phenoxy)phenyl]methane, 1,1-bis[4-(3-maleimide phenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimide phenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimide phenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimide phenoxy)phenyl]ethane, 1,2-bis[ [4-(4-maleimidephenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidephenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidephenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidephenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidephenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidephenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidephenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidephenoxy)biphenyl, 4,4-bis(4-maleimidephenoxy)biphenyl, bis[4 -(3-maleimidephenoxy)phenyl]one, bis[4-(4-maleimidephenoxy)phenyl]one, bis(4-maleimidephenyl)disulfide, bis[4-(3-maleimidephenoxy)phenyl]sulfide, bis[4-(4-maleimidephenoxy)phenyl]sulfide, bis[4-(3-maleimidephenoxy)phenyl]sulfide, bis[4-(3-maleimidephenoxy)phenyl]sulfoxide, bis[4-(4-maleimidephenoxy)phenyl]sulfoxide, bis[4-(3-maleimidephenoxy)phenyl]sulfoxide, bis[4-(4-maleimidephenoxy)phenyl]sulfoxide, bis[4-(3-maleimidephenoxy)phenyl]sulfide, bis[4-(4-maleimidephenoxy)phenyl]sulfide, bis[4-(3-maleimidephenoxy)phenyl]ether, bis[4-(4-maleimidephenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidephenoxy)-α,[α-Dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-Bis[4-(4-maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-Bis[4-(3-maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethane maleimide, biphenyl aralkyl maleimide compounds, etc.

[0296] The modified conjugated diene polymer (B2) preferably has a substituent formed by the reaction of the vinyl group of the conjugated diene polymer (b1) with the N-substituted maleimide group of the maleimide compound (b2) in its side chain [hereinafter, sometimes referred to as "substituent (x)"].

[0297] From the viewpoints of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, the substituent (x) is preferably a group containing the structure shown in the following general formula (B2-11) or (B2-12) as a structure derived from the maleimide compound (b2).

[0298] [Chemical Formula 24]

[0299]

[0300] (where X) B1 To form a divalent group by removing two N-substituted maleimide groups from component (b2),* B1 For the sites where bonds are formed with carbon atoms of vinyl groups present in the side chain of component (b1). B2 (This refers to the site where the atoms bond with each other.)

[0301] The modified conjugated diene polymer (B2) preferably has substituents (x) and vinyl groups (y) on its side chains.

[0302] Regarding the extent to which substituents (x) are present in the modified conjugated diene polymer (B2), the degree to which the vinyl group of component (b1) is modified by component (b2) [hereinafter, sometimes referred to as "vinyl modification rate"]. can be used as an indicator.

[0303] 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 20-70%, more preferably 30-60%, and even more preferably 35-50%. Here, the vinyl modification rate is a value obtained by the method described in the examples.

[0304] Vinyl (y) is preferably derived from the 1,2-vinyl group of the structural unit of butadiene.

[0305] The tensile modulus of elasticity at 25°C of component (B2) is within the preferred range of the tensile modulus of elasticity at 25°C of component (B) described above. However, from the viewpoint of further improving the dielectric properties and conductor adhesion of the obtained resin composition, and from the viewpoint of maintaining good heat resistance, it is preferably 0.01 to 1 GPa, more preferably 0.03 to 0.5 GPa, and even more preferably 0.05 to 0.15 GPa.

[0306] The number average molecular weight of component (B2) is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, it is preferably 700 to 6,000, more preferably 800 to 5,000, and even more preferably 1,000 to 2,500.

[0307] Component (B2) can be manufactured by reacting a conjugated diene polymer (b1) with a maleimide compound (b2).

[0308] There are no particular limitations on the method for reacting the conjugated diene polymer (b1) with the maleimide compound (b2). For example, component (B2) can be obtained by adding the conjugated diene polymer (b1), the maleimide compound (b2), the reaction catalyst and the organic solvent into a reaction vessel, and allowing the reaction to proceed while heating, maintaining the temperature, stirring and so on, as needed.

[0309] From the viewpoint of workability and inhibiting the gelation of products in the reaction, the reaction temperature of the above reaction is preferably 70 to 120°C, more preferably 80 to 110°C, and even more preferably 85 to 105°C.

[0310] From the viewpoint of productivity and full reaction, the reaction time of the above reaction is preferably 0.5 to 15 hours, more preferably 1 to 10 hours, and even more preferably 3 to 7 hours.

[0311] These reaction conditions can be adjusted appropriately according to the type of raw materials used, and there are no particular limitations.

[0312] Examples of organic solvents used in the above reactions include: alcohol solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene; ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0313] One organic solvent can be used alone, or two or more can be used in combination. From the viewpoint of resin solubility, toluene is preferred.

[0314] When the above reaction is carried out in an organic solvent, the total content of the conjugated diene polymer (b1) and maleimide compound (b2) in the reaction solution is not particularly limited, but is preferably 10-70% by mass, more preferably 15-60% by mass, and even more preferably 20-50% by mass. If the total content of the conjugated diene polymer (b1) and maleimide compound (b2) is above the lower limit mentioned above, there is a tendency to obtain a good reaction rate and improve productivity. In addition, if the total content of the conjugated diene polymer (b1) and maleimide compound (b2) is below the upper limit mentioned above, there is a tendency to obtain better solubility, improve stirring efficiency, and further suppress gelation of the product in the reaction.

[0315] From the viewpoint of suppressing gelation of the products in the reaction and obtaining sufficient reactivity, organic peroxides are preferred as reaction catalysts, and α,α'-bis(tert-butylperoxide)diisopropylbenzene is more preferred.

[0316] The reaction catalyst can be used alone or in combination of two or more.

[0317] The amount of reaction catalyst used is not particularly limited. From the viewpoint of reaction rate and reaction uniformity, it is preferably 0.01 to 1 part by mass relative to 100 parts by mass of the total amount of conjugated diene polymer (b1) and maleimide compound (b2), more preferably 0.03 to 0.5 parts by mass, and even more preferably 0.05 to 0.2 parts by mass.

[0318] When the above reaction is carried out, the molar number (M) of N-substituted maleimide groups in the maleimide compound (b2) is... m The molar number of side chain vinyl groups relative to the conjugated diene polymer (b1) (M) v The ratio of (M) m / M vThere are no particular limitations, but from the viewpoint of the compatibility of the obtained (B2) component with other resins and the inhibition of gelation of the products in the reaction, it is preferably 0.001 to 0.5, more preferably 0.005 to 0.1, and even more preferably 0.008 to 0.05.

[0319] [Styrene-based elastomers (B3)]

[0320] (B) The preferred component is a polyolefin resin containing a styrene-based elastomer (B3).

[0321] As for component (B3), there are no particular restrictions as long as the elastomer has a tensile modulus of less than 10 GPa at 25°C and has structural units derived from styrene compounds.

[0322] (B3) Components can be used alone or in combination of two or more.

[0323] As component (B3), it is preferred to have structural units derived from styrene compounds as shown in the following general formula (B3-1).

[0324] [Chemical Formula 25]

[0325]

[0326] (where R is in the formula) b8 R is an alkyl group having 1 to 5 carbon atoms or hydrogen atoms. b9 It is an alkyl group with 1 to 5 carbon atoms. k is an integer from 0 to 5.

[0327] R in the above general formula (B3-1) b8 and R b9 Examples of alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. The alkyl group having 1 to 5 carbon atoms can be either straight-chain or branched. Preferably, it is an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and even more preferably methyl.

[0328] In the above general formula (B3-1), k1 is an integer from 0 to 5, preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0329] The structural units that (B3) has are not derived from styrene compounds, such as structural units derived from butadiene, structural units derived from isoprene, structural units derived from maleic acid, structural units derived from maleic anhydride, etc.

[0330] The structural units derived from butadiene and isoprene described above can be hydrogenated. Upon hydrogenation, the structural units derived from butadiene become structural units composed of a mixture of ethylene and butene units, and the structural units derived from isoprene become structural units composed of a mixture of ethylene and propylene units.

[0331] As component (B3), from the viewpoints of dielectric properties, conductor adhesion, heat resistance, glass transition temperature, and low thermal expansion, it is preferably selected from one or more of styrene-butadiene-styrene block copolymers (SEBS, SBBS), styrene-isoprene-styrene block copolymers (SEPS), and styrene-maleic anhydride copolymers (SMA), more preferably from one or more of styrene-butadiene-styrene block copolymers (SEBS) and styrene-isoprene-styrene block copolymers (SEPS), and even more preferably from styrene-butadiene-styrene block copolymers (SEBS).

[0332] In the aforementioned SEBS, the content of structural units derived from styrene [hereinafter sometimes referred to as "styrene content"] is not particularly limited, but from the viewpoints of dielectric properties, conductor adhesion, heat resistance, glass transition temperature, and low thermal expansion, it is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, and even more preferably 10 to 20% by mass.

[0333] The melt flow rate (MFR) of SEBS is not particularly limited. From the viewpoint of easily adjusting the tensile modulus of elasticity of (B3) component at 25°C to a suitable range, under the test conditions of 230°C and a load of 2.16 kgf (21.2 N), it is preferably 0.1 to 20 g / 10 min, more preferably 1 to 10 g / 10 min, and even more preferably 3 to 7 g / 10 min.

[0334] Examples of SEBS' commercially available products include: TUFTEC (registered trademark) H series and M series manufactured by Asahi Kasei Corporation; SEPTON (registered trademark) series manufactured by KURARAY Corporation; and KRATON (registered trademark) G polymer series manufactured by KRATON POLYMER JAPAN Corporation.

[0335] The tensile modulus of elasticity at 25°C of component (B3) is preferably 0.02 to 4 GPa, more preferably 0.05 to 2 GPa, and even more preferably 0.1 to 1 GPa, from the viewpoint of further improving the dielectric properties and conductor adhesion of the obtained resin composition and maintaining good heat resistance, as described in the preferred range of the tensile modulus of elasticity at 25°C of component (B) above.

[0336] The number-average molecular weight of component (B3) is not particularly limited. From the viewpoint that it is easy to adjust the tensile modulus of elasticity of component (B3) at 25°C to a suitable range, it is preferably 10,000 to 500,000, more preferably 50,000 to 350,000, and even more preferably 100,000 to 200,000.

[0337] The content of one or more selected from components (B1), (B2), and (B3) in the total amount of component (B) is not particularly limited, but from the viewpoint of dielectric properties and conductor adhesion, it is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. The content of one or more selected from components (B1), (B2), and (B3) in the total amount of component (B) is not particularly limited, and may be 100% by mass or less, 98% by mass or less, or 95% by mass or less.

[0338] From the viewpoint of dielectric properties and conductor adhesion, component (B) is preferably a polyolefin resin containing components (B2) and (B3).

[0339] When the polyolefin resin contains (B2) and (B3) components, the content ratio of (B2) to (B3) components [(B2) component / (B3) component] is not particularly limited, but from the viewpoint of compatibility, dielectric properties and conductor adhesion, it is preferably 0.1 to 10, more preferably 0.2 to 5, and even more preferably 0.5 to 1.

[0340] As component (B), polyphenylene ether resin (B4) [hereinafter sometimes referred to as "(B4) component"], silicone resin (B5) [hereinafter sometimes referred to as "(B5) component"], and epoxy resin (B6) [hereinafter sometimes referred to as "(B6) component"].

[0341] (Polyphenylene ether resin (B4))

[0342] As for component (B4), there are no special restrictions as long as it is a polyphenylene ether resin with a tensile elastic modulus of less than 10 GPa at 25°C.

[0343] It should be noted that the term "polyphenylene ether" in this specification includes not only unsubstituted phenylene but also substituted phenylene.

[0344] (B4) Components can be used alone or in combination of two or more.

[0345] Component (B4) also has at least a phenylene ether bond, preferably having the structural unit shown in the following general formula (B4-1).

[0346] [Chemical Formula 26]

[0347]

[0348] (where R is in the formula) b10 It consists of an aliphatic hydrocarbon group or a halogen atom with 1 to 5 carbon atoms. (s1 is an integer from 0 to 4.)

[0349] R in the above general formula (B4-1) b10 Examples of aliphatic hydrocarbon groups with 1 to 5 carbon atoms include alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; and alkenyl and alkynyl groups with 2 to 5 carbon atoms. The aliphatic hydrocarbon group with 1 to 5 carbon atoms can be either straight-chain or branched. Preferably, the aliphatic hydrocarbon group with 1 to 3 carbon atoms is used, more preferably methyl or ethyl, and even more preferably methyl.

[0350] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0351] In the above general formula (B4-1), s1 is an integer from 0 to 4, preferably an integer from 0 to 2, more preferably 1 or 2, and even more preferably 2. When s1 is an integer of 2 or higher, multiple R... b10 They can be the same or different.

[0352] When s1 is 1 or 2, R b10 The substitution is preferably performed at the ortho position on the benzene ring (wherein the substitution position of the oxygen atom is used as a reference).

[0353] The structural unit shown in the above general formula (B4-1) is preferably the structural unit shown in the following general formula (B4-2).

[0354] [Chemical Formula 27]

[0355]

[0356] (B4) Components may or may not have structural units other than phenylene ether units.

[0357] Component (B4) may have phenolic hydroxyl groups at one or both ends. The average number of phenolic hydroxyl groups per molecule of component (B4) is preferably 1 to 2, more preferably 1.4 to 1.9, and even more preferably 1.6 to 1.85.

[0358] From the viewpoints of improving the dielectric properties and conductor adhesion of the obtained resin composition, maintaining good heat resistance, and ease of acquisition, the tensile modulus of (B4) component at 25°C is preferably 0.5 to 7 GPa, more preferably 1 to 5 GPa, and even more preferably 1.5 to 3 GPa.

[0359] The number-average molecular weight of component (B4) is not particularly limited. From the viewpoint that it is easy to adjust the tensile modulus of elasticity of component (B4) at 25°C to a suitable range, it is preferably 1,000 to 50,000, more preferably 5,000 to 20,000, and even more preferably 8,000 to 15,000.

[0360] (Organosilicon resin (B5))

[0361] As for component (B5), there are no particular restrictions as long as it is an organosilicon resin with a tensile elastic modulus of less than 10 GPa at 25°C.

[0362] (B5) Components can be used alone or in combination of two or more.

[0363] (B5) component has at least a siloxane bond, preferably a structural unit as shown in the following general formula (B5-1).

[0364] [Chemical Formula 28]

[0365]

[0366] (where R is in the formula) b11 and R b12 Each of the following is independently an alkyl, phenyl, or phenyl group having 1 to 5 carbon atoms.

[0367] R in the above general formula (B5-1) b11 and R b12 Examples of alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. The alkyl group having 1 to 5 carbon atoms can be either straight-chain or branched. Preferably, the alkyl group has 1 to 3 carbon atoms; more preferably, methyl or ethyl; and even more preferably, methyl.

[0368] R in the above general formula (B5-1) b11 and R b12The substituents in the phenyl group represented by the substituent can be, for example, alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms, or alkynyl groups having 2 to 5 carbon atoms. Examples of alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. Examples of alkenyl groups having 2 to 5 carbon atoms include vinyl and allyl. Examples of alkynyl groups having 2 to 5 carbon atoms include ethynyl and propargyl. The alkyl groups having 1 to 5 carbon atoms, the alkenyl groups having 2 to 5 carbon atoms, and the alkynyl groups having 2 to 5 carbon atoms can be either straight-chain or branched.

[0369] In the above general formula (B5-1), R b11 and R b12 Preferably, they are alkyl groups having 1 to 5 carbon atoms, more preferably methyl or ethyl, and even more preferably methyl.

[0370] That is, the structural unit shown in the above general formula (B5-1) is preferably a dimethylsiloxane unit.

[0371] (B5) The component can be a linear organosilicon resin or a branched organosilicon resin, preferably a linear organosilicon resin.

[0372] (B5) Components may have reactive groups in their molecular structure. These reactive groups may be incorporated into the side chain of the polysiloxane, or into one or both ends of the polysiloxane. Furthermore, reactive groups may be incorporated into the side chain of the polysiloxane, or into one or both ends.

[0373] Examples of the reactive groups mentioned above include epoxy, amino, vinyl, hydroxy, methacryloyl, mercapto, carboxyl, alkoxy, and silanol groups. (B5) Components may contain one or more of the reactive groups mentioned above.

[0374] Among them, amino and vinyl groups are preferred as reactive groups. Among amino groups, primary amino and secondary amino groups are preferred, and primary amino groups are more preferred.

[0375] When component (B5) contains amino groups, from the viewpoint of compatibility with other resins, component (B5) preferably has one or two primary amino groups, more preferably two primary amino groups, and even more preferably a diamino polysiloxane having one primary amino group at each end.

[0376] The tensile modulus of elasticity at 25°C of component (B5) is within the preferred range of the tensile modulus of elasticity at 25°C of component (B) described above. However, from the viewpoint of further improving the dielectric properties and conductor adhesion of the obtained resin composition, and from the viewpoint of maintaining good heat resistance, it is preferably 0.01 to 1 GPa, more preferably 0.03 to 0.5 GPa, and even more preferably 0.05 to 0.15 GPa.

[0377] When component (B5) has reactive groups, the amount of reactive group equivalent is not particularly limited, but is preferably 200 to 3,000 g / mol, more preferably 300 to 1,000 g / mol, and even more preferably 400 to 600 g / mol.

[0378] (Epoxy Resin (B6))

[0379] As for component (B6), there are no special restrictions as long as the epoxy resin has a tensile modulus of elasticity of less than 10 GPa at 25°C.

[0380] (B6) Components can be used alone or in combination of two or more.

[0381] As component (B6), epoxy resin having two or more epoxy groups is preferred. Epoxy resins are classified as glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.

[0382] Examples of components (B6) include aliphatic chain epoxy resins, rubber-modified epoxy resins, and epoxy resins having an alicyclic backbone. Among these, epoxy resins having an alicyclic backbone are preferred from the viewpoint of improving the dielectric properties and conductor adhesion of the obtained resin composition.

[0383] The alicyclic skeleton of component (B6) is not particularly limited, but an alicyclic skeleton with 5 to 20 carbon atoms is preferred, an alicyclic skeleton with 6 to 18 carbon atoms is even more preferred, and an alicyclic skeleton with 8 to 14 carbon atoms is particularly preferred.

[0384] Furthermore, the aforementioned alicyclic skeleton preferably contains two or more rings, more preferably two to four rings, and even more preferably three rings. Examples of alicyclic skeletons containing two or more rings include norbornene skeleton, decahydronaphthalene skeleton, bicycloundecane skeleton, and dicyclopentadiene skeleton.

[0385] The preferred alicyclic skeleton is the dicyclopentadiene skeleton.

[0386] Examples of epoxy resins having an alicyclic backbone include epoxy resins represented by the following general formula (B6-1).

[0387] [Chemical Formula 29]

[0388]

[0389] (where R is in the formula) b13 It is an alkyl group having 1 to 12 carbon atoms, and can be substituted at any position in the above-described alicyclic skeleton. R b14 It is an alkyl group with 1 to 12 carbon atoms. m1 is an integer from 0 to 6, m2 is an integer from 0 to 3, and r is a number from 0 to 10.

[0390] R in the above general formula (B6-1) b13 Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. These alkyl groups can be either straight-chain or branched. Preferably, the alkyl group has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and methyl is even more preferred.

[0391] In the above general formula (B6-1), m1 is an integer from 0 to 6, preferably an integer from 0 to 5, more preferably an integer from 0 to 2, and even more preferably 0.

[0392] When m1 is an integer greater than 2, multiple R b13 They can be the same or different from each other. Furthermore, multiple R... b13 Substitution can be performed on the same carbon atom or on different carbon atoms, within the possible range.

[0393] R in the above general formula (B6-1) b14 Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. These alkyl groups can be either straight-chain or branched. Preferably, the alkyl group has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and methyl is even more preferred.

[0394] In the above general formula (B6-1), m2 is an integer from 0 to 3, preferably 0 or 1, and more preferably 0.

[0395] When m² is an integer greater than 2, multiple R b14 They can be the same or different.

[0396] In the above general formula (B6-1), r represents the number of repetitions of the structural unit within the parentheses, which is a number from 0 to 10, preferably from 2 to 10. When the epoxy resin shown in the above general formula (B6-1) is a mixture of epoxy resins with different numbers of repetitions of the structural unit within the parentheses, r represents the average value of the mixture.

[0397] From the viewpoints of improving the dielectric properties and conductor adhesion of the obtained resin composition, maintaining good heat resistance, and ease of acquisition, the tensile modulus of elasticity of component (B6) at 25°C is preferably 1 to 7 GPa, more preferably 1.5 to 5 GPa, and even more preferably 2 to 3 GPa.

[0398] The amount of epoxy group equivalent as component (B6) is not particularly limited, but is preferably 150 to 1,000 g / mol, more preferably 200 to 500 g / mol, and even more preferably 250 to 300 g / mol.

[0399] (Other (B) components)

[0400] As a component other than those mentioned above (B), for example, one or more selected from polyurethane resins, polyester resins, polyamide resins and polyacrylic resins may be included.

[0401] Examples of polyurethane resins include polyurethane resins having hard segments formed from low molecular weight diols and diisocyanates, and soft segments formed from high molecular weight diols and diisocyanates.

[0402] Examples of low-molecular-weight diols include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. Examples of high-molecular-weight diols include polypropylene glycol, polytetrahydrofuran, poly(1,4-butanediol adipate), poly(ethylene-1,4-butanediol adipate), polycaprolactone, poly(1,6-hexanediol carbonate), and poly(1,6-hexene-neopentylene adipate). Low-molecular-weight diols and high-molecular-weight diols can each be used individually or in combination of two or more.

[0403] Polyurethane resins can be used alone or in combination of two or more.

[0404] Examples of polyester resins include polyester resins obtained by polycondensation of dicarboxylic acid or its derivatives with diol compounds or their derivatives.

[0405] Examples of dicarboxylic acids include: aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; aromatic dicarboxylic acids in which the hydrogen atoms of the aromatic nucleus are replaced by methyl, ethyl, phenyl, etc.; aliphatic dicarboxylic acids with 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These dicarboxylic acids can be used alone or in combination of two or more.

[0406] Examples of diol compounds include: aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol; alicyclic diols such as 1,4-cyclohexanediol; and aromatic diols such as bisphenol A, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)propane, and resorcinol. These diol compounds can be used alone or in combination of two or more.

[0407] Alternatively, a multiblock copolymer can be used, in which aromatic polyester components such as polybutylene terephthalate are used as hard segment components and aliphatic polyester components such as polytetramethylene glycol are used as soft segment components.

[0408] Polyester resins can be used alone or in combination of two or more.

[0409] Examples of polyamide-based resins include block copolymers in which polyamide is used as a hard segment component, and polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene-propylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate, polymethacrylate, polyurethane, silicone rubber, etc. are used as soft segment components.

[0410] Polyamide resins can be used alone or in combination of two or more.

[0411] Examples of acrylic resins include polymers formed by polymerizing monomers primarily composed of acrylates. Examples of acrylates include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate. Crosslinking monomers can be those using glycidyl methacrylate, allyl glycidyl ether, etc., as raw materials; alternatively, they can be crosslinking monomers copolymerized from acrylonitrile, ethylene, etc. Specifically, examples include acrylonitrile-butyl acrylate copolymers, acrylonitrile-butyl acrylate-ethyl acrylate copolymers, and acrylonitrile-butyl acrylate-glycidyl methacrylate copolymers.

[0412] Acrylic resins can be used alone or in combination of two or more.

[0413] <The content of component (A) and component (B), and their proportions>

[0414] In the resin composition of this embodiment, the content of component (A) is not particularly limited, but is preferably 10 to 90 parts by mass relative to 100 parts by mass of the total resin components in the resin composition of this embodiment, more preferably 20 to 80 parts by mass, and even more preferably 25 to 75 parts by mass. If the content of component (A) is above the lower limit mentioned above, there is a tendency for improved heat resistance, formability, processability, flame retardancy, and conductor adhesion. In addition, if the content of component (A) is below the upper limit mentioned above, there is a tendency for improved dielectric properties.

[0415] Furthermore, the content of component (A) is not particularly limited. From the viewpoint of further improving heat resistance, etc., it can be 30 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more, relative to 100 parts by mass of the total resin components in the resin composition of this embodiment.

[0416] Furthermore, the content of component (A) is not particularly limited. From the viewpoint of further improving dielectric properties, etc., the content can be 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less, relative to 100 parts by mass of the total resin components in the resin composition of this embodiment.

[0417] In this specification, "resin component" refers to resin and compounds that form resin through a curing reaction. For example, components (A) and (B) are equivalent to resin components. Furthermore, if the resin composition of this embodiment contains resin or compounds that form resin through a curing reaction as optional components in addition to components (A) and (B), these optional components are also included in the resin component. Components (C), (D), and (E), described later, are not included in the resin component.

[0418] In the resin composition of this embodiment, the content of component (B) is not particularly limited, but is preferably 10 to 90 parts by mass relative to 100 parts by mass of the total resin components in the resin composition of this embodiment, more preferably 20 to 80 parts by mass, and even more preferably 25 to 75 parts by mass. If the content of component (B) is above the lower limit mentioned above, the dielectric properties tend to be better. In addition, if the content of component (B) is below the upper limit mentioned above, the heat resistance, formability, processability, flame retardancy, and conductor adhesion tend to be better.

[0419] Furthermore, the content of component (B) is not particularly limited. From the viewpoint of further improving dielectric properties, etc., it can be 30 parts by mass or more, 40 parts by mass or more, or 50 parts by mass or more, relative to 100 parts by mass of the total resin components in the resin composition of this embodiment.

[0420] Furthermore, the content of component (B) is not particularly limited. From the viewpoint of further improving heat resistance, etc., the content can be 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less, relative to 100 parts by mass of the total resin components in the resin composition of this embodiment.

[0421] In the resin composition of this embodiment, the content ratio of component (A) to component (B) [(A) / (B)] is not particularly limited, but is preferably 0.1 to 9 by mass, more preferably 0.25 to 4, and even more preferably 0.3 to 3. If the content ratio of component (A) to component (B) [(A) / (B)] is above the lower limit value mentioned above, there is a tendency for improved heat resistance, formability, processability, flame retardancy, and conductor adhesion. In addition, if the content ratio of component (A) to component (B) [(A) / (B)] is below the upper limit value mentioned above, there is a tendency for improved dielectric properties.

[0422] Furthermore, the content ratio of component (A) to component (B) [(A) / (B)] is not particularly limited. From the viewpoint of further improving heat resistance and other properties, it can be 0.5 or more, 1 or more, or 1.5 or more on a mass basis.

[0423] Furthermore, the content ratio of component (A) to component (B) [(A) / (B)] is not particularly limited. From the viewpoint of further improving dielectric properties, etc., it can be 7 or less, 2 or less, 1 or less, or 0.6 or less based on mass.

[0424] The content of resin component in the resin composition of this embodiment is not particularly limited, but from the viewpoint of low thermal expansion, elastic modulus, heat resistance, flame retardancy and conductor adhesion, it is preferably 10 to 70% by mass, more preferably 20 to 65% by mass, and even more preferably 30 to 60% by mass.

[0425] <Other Ingredients>

[0426] The resin composition of this embodiment may be further contained with other components depending on the desired performance.

[0427] Other components may include, for example, one or more selected from inorganic filler (C) [hereinafter sometimes referred to as "(C) component"]., flame retardant (D) [hereinafter sometimes referred to as "(D) component"]., and curing accelerator (E) [hereinafter sometimes referred to as "(E) component"].

[0428] However, the resin composition of this embodiment may also be without one or more of the inorganic filler (C), flame retardant (D), and curing accelerator (E) depending on the desired performance.

[0429] The following is a detailed description of these components.

[0430] (Inorganic filler material (C))

[0431] The resin composition of this embodiment tends to have further improved low thermal expansion, elastic modulus, heat resistance and flame retardancy by containing inorganic filler (C).

[0432] Inorganic filler material (C) can be used alone or in combination of two or more types.

[0433] Examples of inorganic filler materials (C) include silica, alumina, titanium dioxide, mica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, and silicon carbide. Among these, silica, alumina, mica, and talc are preferred from the viewpoints of low thermal expansion, elastic modulus, heat resistance, and flame retardancy; silica and alumina are more preferred; and silica is even more preferred.

[0434] Examples of silica include: precipitated silica with high water content produced by wet processing, and dry silica produced by dry processing that contains almost no bound water. Dry silica can be further categorized into, depending on the manufacturing method, such as crushed silica, fumed silica, and molten silica.

[0435] The average particle size of the inorganic filler material (C) is not particularly limited, but from the viewpoint of dispersibility and fine wiring, it is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, even more preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm.

[0436] In this specification, the average particle size of the inorganic filler material (C) refers to the particle size at a point corresponding to 50% of the volume when the total volume of the particles is set to 100% and a cumulative frequency distribution curve based on particle size is obtained. The particle size of the inorganic filler material (C) can be measured, for example, using a particle size distribution measuring device employing laser diffraction scattering.

[0437] The shape of the inorganic filler material (C) can be, for example, spherical or fragmented, but spherical is preferred.

[0438] When the resin composition of this embodiment contains inorganic filler (C), the content of inorganic filler (C) in the resin composition is not particularly limited. From the viewpoints of low thermal expansion, elastic modulus, heat resistance and flame retardancy, it is preferably 10 to 70% by mass relative to the total solid content (100% by mass) of the resin composition, more preferably 20 to 65% by mass, and even more preferably 30 to 60% by mass.

[0439] In the case where the resin composition of this embodiment contains inorganic filler (C), a coupling agent can be used to improve the dispersibility of the inorganic filler (C) and its adhesion to the organic components. Examples of coupling agents include silane coupling agents and titanate coupling agents. Among these, silane coupling agents are preferred. Examples of silane coupling agents include aminosilane coupling agents, vinylsilane coupling agents, and epoxysilane coupling agents.

[0440] When a coupling agent is used in the resin composition of this embodiment, the surface treatment method for the inorganic filler (C) can be a general mixing treatment method in which the coupling agent is added after the inorganic filler (C) is incorporated into the resin composition, or it can be a method of pre-treating the inorganic filler (C) with the coupling agent in a dry or wet manner. From the viewpoint of more effectively showcasing the advantages of the inorganic filler (C), the method of pre-treating the inorganic filler (C) with the coupling agent in a dry or wet manner is preferred.

[0441] For the purpose of improving dispersibility in resin compositions, inorganic filler (C) can be pre-prepared as a slurry dispersed in an organic solvent and then mixed with other components.

[0442] (Flame retardant (D))

[0443] The resin composition of this embodiment tends to have further improved flame retardancy by containing a flame retardant (D).

[0444] Flame retardant (D) can be used alone or in combination of two or more.

[0445] In addition, the resin composition of this embodiment may contain flame retardant additives as needed.

[0446] As flame retardants (D), examples include phosphorus-based flame retardants, metal hydrates, and halogen-based flame retardants. From an environmental perspective, phosphorus-based flame retardants and metal hydrates are preferred.

[0447] -Phosphorus-based flame retardants-

[0448] As a phosphorus-based flame retardant, there are no particular limitations on the type of substance containing phosphorus atoms that is commonly used as a flame retardant; it can be either inorganic or organic. It should be noted that, from an environmental perspective, phosphorus-based flame retardants are preferably free of halogen atoms.

[0449] Examples of inorganic phosphorus-based flame retardants include: red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen- and phosphorus-containing compounds such as phosphoric acid amide; phosphoric acid; and phosphine oxide.

[0450] Examples of organic phosphorus-based flame retardants include aromatic phosphates, monosubstituted phosphonate diesters, disubstituted hypophosphite esters, metal salts of disubstituted hypophosphite, organic nitrogen- and phosphorus-containing compounds, and cyclic organophosphorus compounds. Among these, aromatic phosphate compounds and metal salts of disubstituted hypophosphite are preferred. Examples of metal salts include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts. Aluminum salts are preferred. Furthermore, aromatic phosphates are preferred among organic phosphorus-based flame retardants.

[0451] Examples of aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, tri(xyl) phosphate, toluene diphenyl phosphate, toluene di-2,6-dimethyl phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(di-2,6-dimethyl phosphate), bisphenol A-bis(diphenyl phosphate), and 1,3-phenylene bis(diphenyl phosphate).

[0452] Examples of monosubstituted phosphonic acid diesters include diethylene phenylphosphonate, diallyl phenylphosphonate, and bis(1-butenyl) phenylphosphonate.

[0453] Examples of 2-substituted phosphonates include phenyl diphenylphosphonate and methyl diphenylphosphonate.

[0454] Examples of metal salts of dialkylphosphinic acid include metal salts of dialkylphosphinic acid, diallylphosphinic acid, divinylphosphinic acid, and diarylphosphinic acid. Aluminum salts are preferred among these metal salts.

[0455] Examples of organic nitrogen- and phosphorus-containing compounds include: bis(2-allylphenoxy)phosphazene, xylylphosphazene and other phosphazene compounds; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; melamine polyphosphate, etc.

[0456] Examples of cyclic organophosphorus compounds include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0457] Among the above organic phosphorus-based flame retardants, aromatic phosphate esters and metal salts of 2-substituted phosphonic acids are preferred, 1,3-phenylenebis(di-2,6-dimethyl phosphate) and aluminum salts of dialkylphosphonic acids are more preferred, and tri(diethylphosphonic acid)aluminum is even more preferred.

[0458] -Metal hydrates-

[0459] Examples of metal hydrates include aluminum hydroxide hydrate and magnesium hydroxide hydrate.

[0460] -Halogen-based flame retardants-

[0461] Examples of halogen-based flame retardants include chlorine-based and brominated flame retardants. Examples of chlorine-based flame retardants include chlorinated paraffins.

[0462] When the resin composition of this embodiment contains a flame retardant (D), the content of the flame retardant (D) is not particularly limited. It is preferably 1 to 15 parts by mass relative to 100 parts by mass of the total resin components in the resin composition of this embodiment, more preferably 4 to 12 parts by mass, and even more preferably 6 to 10 parts by mass. If the content of the flame retardant (D) is above the aforementioned lower limit, the flame retardancy tends to improve. Furthermore, if the content of the flame retardant (D) is below the aforementioned upper limit, the formability, conductor adhesion, heat resistance, and glass transition temperature tend to improve.

[0463] Examples of flame retardant additives include inorganic flame retardants such as antimony trioxide and zinc molybdate.

[0464] When the resin composition of this embodiment contains a flame retardant additive, its content is not particularly limited. It is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total resin components in the resin composition of this embodiment, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass. If the content of the flame retardant additive is within the above range, there is a tendency to obtain better chemical resistance.

[0465] (Cure Accelerator (E))

[0466] The resin composition of this embodiment tends to have improved curability, dielectric properties, heat resistance, conductor adhesion, elastic modulus and glass transition temperature by containing a curing accelerator (E).

[0467] Curing accelerator (E) can be used alone or in combination of two or more.

[0468] Examples of curing accelerators (E) include: acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazolium and phenylimidazolium; isocyanate-masked imidazole compounds such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazolium; tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexyn-3, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane, tert-butylperoxide isopropyl monocarbonate, and α,α'-bis(tert-butylperoxide)diisopropylbenzene; and carboxylates of manganese, cobalt, zinc, etc.

[0469] From the viewpoints of heat resistance, glass transition temperature and storage stability, the preferred materials are imidazole compounds, isocyanate-masked imidazole compounds, organic peroxides, and carboxylates, more preferably organic peroxides, and even more preferably diisopropylbenzene peroxide.

[0470] When the resin composition of this embodiment contains a curing accelerator (E), the content of the curing accelerator (E) is not particularly limited. It is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the total resin components in the resin composition of this embodiment, more preferably 0.1 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass. If the content of the curing accelerator (E) is above the lower limit mentioned above, there is a tendency for improved dielectric properties, heat resistance, conductor adhesion, elastic modulus, and glass transition temperature. Furthermore, if the content of the curing accelerator (E) is below the upper limit mentioned above, there is a tendency for improved storage stability.

[0471] The resin composition of this embodiment may further contain, as needed, one or more of the following components selected from resin materials, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and additives other than those mentioned above.

[0472] Each of the above ingredients can be used alone or in combination of two or more.

[0473] The content of any of the above-mentioned components in the resin composition of this embodiment is not particularly limited, and can be used as needed within a range that does not hinder the effect of this embodiment.

[0474] Furthermore, the resin composition of this embodiment may also be without any of the above-mentioned components, depending on the desired performance.

[0475] (Organic solvents)

[0476] From the viewpoint of ease of operation and ease of manufacturing the prepreg described later, the resin composition of this embodiment may contain an organic solvent.

[0477] Organic solvents can be used alone or in combination of two or more.

[0478] It should be noted that in this specification, resin compositions containing organic solvents are sometimes referred to as resin varnishes.

[0479] Examples of organic solvents 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-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and ester solvents such as γ-butyrolactone.

[0480] From the viewpoint of solubility, alcohol solvents, ketone solvents, nitrogen-containing solvents, and aromatic hydrocarbon solvents are preferred, aromatic hydrocarbon solvents are more preferred, and toluene is even more preferred.

[0481] In the case where the resin composition of this embodiment contains an organic solvent, the concentration of the solids component of the resin composition is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and even more preferably 40 to 60% by mass. If the solids component concentration is within the above range, the processability of the resin composition becomes easier, and the impregnation of the substrate and the appearance of the manufactured prepreg tend to be better. Furthermore, the adjustment of the solids component concentration of the resin in the prepreg, as described later, becomes easier, and the manufacture of prepregs with the desired thickness becomes more convenient.

[0482] The resin composition of this embodiment can be manufactured by mixing component (A) and component (B), along with other components to be used in combination as needed, using a known method. During mixing, each component can be dissolved or dispersed while stirring. Furthermore, there are no particular limitations on the order of mixing raw materials, mixing temperature, mixing time, etc., and these conditions can be arbitrarily set according to the type of raw materials.

[0483] The relative permittivity (Dk) of the cured resin composition of this embodiment at 10 GHz is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably 2.8 or less. The smaller the relative permittivity (Dk) mentioned above, the more preferred it is. There is no particular limitation on its lower limit value. Considering the balance with other properties, it can be 2.3 or more, 2.4 or more, or 2.5 or more.

[0484] The conditions for obtaining a cured product from the resin composition of this embodiment can be set as described in the examples.

[0485] The aforementioned relative permittivity (Dk) is a value obtained based on the cavity resonator perturbation method, and more specifically, a value measured by the method described in the embodiments.

[0486] The dielectric loss tangent (Df) of the cured resin composition of this embodiment at 10 GHz is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 0.0040 or less, more preferably 0.0030 or less, and even more preferably 0.0020 or less. The smaller the dielectric loss tangent (Df) mentioned above, the more preferred it is. There is no particular limitation on its lower limit value. Considering the balance with other physical properties, it can be, for example, 0.0010 or more, 0.0012 or more, or 0.0014 or more.

[0487] The conditions for obtaining a cured product from the resin composition of this embodiment can be set as described in the examples.

[0488] The dielectric loss tangent (Df) mentioned above is a value obtained based on the cavity resonator perturbation method, and more specifically, a value measured by the method described in the embodiments.

[0489] [Prepreg]

[0490] The prepreg in this embodiment is a prepreg containing the resin composition of this embodiment or a semi-cured product of the above-described resin composition.

[0491] That is, the prepreg of this embodiment can also be said to be made containing the resin composition of this embodiment. It should be noted that, in this specification, "made containing..." means a substance formed at least in a state of containing.

[0492] The prepreg in this embodiment contains, for example, the resin composition of this embodiment or a semi-cured product of the above-described resin composition and a sheet fiber substrate.

[0493] There are no particular limitations on sheet fiber substrates, but sheet fiber reinforced substrates used for reinforcing prepregs are preferred.

[0494] As the sheet fiber substrate contained in the prepreg of this embodiment, known sheet fiber substrates used in various electrical insulation material laminates can be used.

[0495] Materials used as sheet fiber substrates include, for example, 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 fiber substrates can take the form of fabrics, nonwovens, rovings, chopped strand mats, and surface mats.

[0496] The thickness of the sheet fiber substrate is not particularly limited, but from the viewpoint of mechanical strength and thinning of the prepreg, it is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and even more preferably 0.03 to 0.1 mm.

[0497] From the perspective of the impregnation properties of the resin composition, the heat resistance, moisture resistance and processability when the laminate is made, the sheet fiber substrate can be a sheet fiber substrate that has been surface treated with coupling agents or the like, or a sheet fiber substrate that has undergone mechanical fiber opening treatment.

[0498] The prepreg of this embodiment can be manufactured, for example, by impregnating or coating the resin composition of this embodiment onto a sheet fiber substrate and then drying it as needed.

[0499] Methods for impregnating or coating a resin composition onto a sheet fiber substrate include, for example, hot melt methods and solvent methods.

[0500] The hot-melt method is a method of impregnating or coating a resin composition that does not contain organic solvents onto a sheet-like fiber substrate. One example of the hot-melt method is to temporarily coat the resin composition onto a peelable coated paper and then laminate the coated resin composition onto the sheet-like fiber substrate. Another example of the hot-melt method is to directly coat the resin composition onto the sheet-like fiber substrate using a die-coating machine.

[0501] The solvent method involves impregnating or coating a resin composition containing an organic solvent onto a sheet-like fiber substrate. Specifically, an example is a method of impregnating a sheet-like fiber substrate in a resin composition containing an organic solvent followed by drying. By drying, the organic solvent is removed, and the resin composition is semi-cured (B-stage curing), resulting in the prepreg of this embodiment.

[0502] The concentration of solid components from the resin composition in the prepreg of this embodiment is not particularly limited, but from the viewpoint that better formability can be obtained when making laminates, it is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and even more preferably 30 to 75% by mass.

[0503] The thickness of the prepreg in this embodiment is not particularly limited, but from the viewpoint of formability and the ability to perform high-density wiring, it is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and even more preferably 0.03 to 0.1 mm.

[0504] [Resin film]

[0505] The resin film of this embodiment is a resin film containing the resin composition of this embodiment or a semi-cured product of the above-described resin composition.

[0506] That is, the resin film of this embodiment can also be said to be made of the resin composition of this embodiment.

[0507] The resin film of this embodiment can be manufactured, for example, by coating a support with the resin composition of this embodiment containing an organic solvent, i.e., a resin varnish, and then heating and drying it.

[0508] Examples of suitable supports include plastic film, metal foil, and release paper.

[0509] Examples of plastic films include: films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate; polycarbonate films; and polyimide films.

[0510] Examples of metal foils include copper foil and aluminum foil.

[0511] The support can be a support that has undergone surface treatments such as matte finish or corona treatment. Alternatively, the support can also be a support that has undergone release treatment using silicone resin-based release agents, alkyd resin-based release agents, fluoropolymer-based release agents, etc.

[0512] The thickness of the support is not particularly limited, but from the viewpoint of processability and economy, it is preferably 10 to 150 μm, more preferably 20 to 100 μm, and even more preferably 25 to 50 μm.

[0513] As a coating apparatus for applying resin varnishes, one can use, for example, a comma coater, a bar coater, a coincidence coater, a roller coater, a gravure coater, a die coater, or other coating apparatus known to those skilled in the art. These coating apparatuses can be selected appropriately based on the desired film thickness.

[0514] The drying conditions after applying resin varnish can be determined appropriately based on the content of organic solvent, boiling point, etc., without any particular limitation.

[0515] For example, in the case of a resin varnish containing 40 to 60% by mass of an aromatic hydrocarbon solvent, the drying temperature is not particularly limited. From the viewpoint of productivity and to moderately B-stage the resin composition of this embodiment, it is preferably 50 to 200°C, more preferably 100 to 190°C, and even more preferably 150 to 180°C.

[0516] Furthermore, in the case of the above-mentioned resin varnish, the drying time is not particularly limited. From the viewpoint of productivity and to moderately B-stage the resin composition of this embodiment, it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and even more preferably 3 to 10 minutes.

[0517] [Laminated Board]

[0518] The laminate of this embodiment is a laminate having a cured resin composition of this embodiment or a cured prepreg and having a metal foil.

[0519] That is, the laminate of this embodiment can also be said to be made of the resin composition or prepreg of this embodiment and metal foil.

[0520] It should be noted that laminates with metal foil are sometimes also called metal-clad laminates.

[0521] The metal used as the foil is not particularly limited, but from the viewpoint of electrical conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements are preferred, copper and aluminum are more preferred, and copper is even more preferred.

[0522] The laminated board of this embodiment can be manufactured, for example, by heat-pressing and forming a prepreg with metal foil on one or both sides. In this case, only one sheet of prepreg can be used, or two or more sheets can be laminated.

[0523] The heating temperature for heating and pressing is not particularly limited, but is preferably 100-300°C, more preferably 150-280°C, and even more preferably 200-250°C.

[0524] The heating and pressurizing time for heating and pressurizing is not particularly limited, but is preferably 10 to 300 minutes, more preferably 30 to 200 minutes, and even more preferably 80 to 150 minutes.

[0525] The pressure for heating and pressing is not particularly limited, but is preferably 1.5 to 5 MPa, more preferably 1.7 to 3 MPa, and even more preferably 1.8 to 2.5 MPa.

[0526] These conditions can be adjusted appropriately based on the type of raw materials used, and there are no particular limitations.

[0527] Printed Circuit Board

[0528] The printed circuit board of this embodiment is a printed circuit board having one or more of the following: a cured product of the resin composition of this embodiment, a cured product of the prepreg of this embodiment, and a laminate of this embodiment.

[0529] That is, the printed circuit board of this embodiment can also be said to be made of one or more of the resin composition selected from this embodiment, the prepreg of this embodiment, and the laminate of this embodiment.

[0530] The printed circuit board of this embodiment has at least: a conductor circuit layer; and a structure containing a cured resin composition of this embodiment, a cured prepreg of this embodiment, or a laminate of this embodiment.

[0531] The printed circuit board of this embodiment can be manufactured, for example, by forming conductor circuits on one or more of the following methods: a cured resin composition of this embodiment, a cured prepreg of this embodiment, a cured resin film of this embodiment, and a laminate of this embodiment. Alternatively, a multilayer printed circuit board can be manufactured by further performing multilayer bonding processes as needed. Conductor circuits can be formed, for example, by appropriately performing hole-making, metal plating, or etching of metal foil.

[0532] [Semiconductor Package]

[0533] The semiconductor package of this embodiment is a semiconductor package having a printed circuit board and semiconductor elements as described in this embodiment. For example, the semiconductor package of this embodiment can be manufactured by mounting semiconductor elements, memory, etc., on the printed circuit board of this embodiment using known methods.

[0534] Example

[0535] The following examples illustrate this implementation method in detail. However, this implementation method is not limited to the following examples.

[0536] It should be noted that, in each case, the number-average molecular weight was determined according to the following steps.

[0537] (Methods for determining number-average molecular weight)

[0538] Number-average molecular weight was calculated by gel permeation chromatography (GPC) based on a standard curve using standard polystyrene. The standard curve used standard polystyrene: TSKstandard POLYSTYRENE (models: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name], approximated by a cubic formula. The determination conditions for GPC are shown below.

[0539] [GPC Measurement Conditions]

[0540] Device: High-speed GPC device HLC-8320GPC

[0541] Detector: UV-8320 ultraviolet absorbance detector [manufactured by Tosoh Corporation]

[0542] Pillars: Protective pillars: TSK Guardcolumn SuperHZ-L + Pillars: TSKgel SuperHZM-N + TSKgel SuperHZM-M + TSKgel SuperH-RC (All manufactured by Tosoh Corporation, product names)

[0543] Column dimensions: 4.6×20mm (protective column), 4.6×150mm (column), 6.0×150mm (reference column)

[0544] Eluent: Tetrahydrofuran

[0545] Sample concentration: 10 mg / 5 mL

[0546] Injection volume: 25μL

[0547] Flow rate: 1.00 mL / min

[0548] Measurement temperature: 40℃

[0549] (Determination of vinyl modification rate)

[0550] In the manufacturing example described later, GPC was measured using the above method for both the solution containing components (b1) and (b2) before the reaction and the solution after the reaction, to determine the peak area from component (b2) before and after the reaction. Next, the vinyl modification rate of component (b2) was calculated using the following formula. It should be noted that the vinyl modification rate is equivalent to the rate of decrease in the peak area from component (b2) caused by the reaction.

[0551] Vinyl modification rate (%) = [(peak area from component (b2) before the reaction starts) - (peak area from component (b2) after the reaction ends)] × 100 / (peak area from component (b2) before the reaction starts)

[0552] (Determination of tensile modulus of elasticity at 25℃)

[0553] A test piece with a width of 10 mm, a length of 80 mm, and a thickness of 0.2 mm was prepared from the resin to be tested. The test piece was clamped at both ends along its long side using upper and lower clamps spaced 60 mm apart. Next, using an Autograph (manufactured by Shimadzu Corporation, AG-X), the tensile modulus of elasticity at 25°C was obtained at a room temperature of 25°C and a tensile speed of 5 mm / min. Five identical test pieces were prepared, and their tensile modulus of elasticity at 25°C was obtained under the same conditions. The average value of these samples was taken as the tensile modulus of elasticity at 25°C for the resin. Other detailed conditions and the method for calculating the tensile modulus of elasticity were performed according to international standard ISO 5271 (1993).

[0554] [Preparation of modified conjugated diene polymers]

[0555] Manufacturing Examples 1-2

[0556] The raw materials and toluene as an organic solvent were added to a 2L glass flask equipped with a thermometer, reflux condenser, and stirrer, capable of both heating and cooling. Next, the mixture was reacted under a nitrogen atmosphere at 90–100°C with stirring for 5 hours, thereby obtaining solutions of modified conjugated diene polymers 1 and 2 (solids concentration: 35% by mass). The vinyl modification rate and number-average molecular weight of the obtained modified conjugated diene polymers are shown in Table 1.

[0557] [Table 1]

[0558] Table 1

[0559]

[0560] It should be noted that the details of each component recorded in Table 1 are as follows.

[0561] [(b1) Ingredients]

[0562] • Polybutadiene 1:1,2-polybutadiene homopolymer, number average molecular weight = 1,200, vinyl content = ≥ 85%

[0563] [(b2) Components]

[0564] • Bismaleimide compound 1: An aromatic bismaleimide compound containing an indenyl ring (number average molecular weight = 1,300)

[0565] • Bismaleimide compound 2: bis(3-ethyl-5-methyl-4-maleimidephenyl)methane

[0566] [Reaction Catalyst]

[0567] • Organic peroxide: α,α'-bis(tert-butylperoxide)diisopropylbenzene

[0568] [Preparation of Resin Composition]

[0569] Examples 1-8, Comparative Examples 1-3

[0570] The components listed in Table 2 are combined with toluene according to the proportions listed in Table 2, and then stirred and mixed at 25°C or heated to 50–80°C to prepare a resin composition with a solid component concentration of approximately 50% by mass. It should be noted that the proportions of each component in Table 2 are in parts by mass; in the case of a solution, they refer to the parts by mass converted from solid components.

[0571] [Manufacturing of resin film and resin board with copper foil on both sides]

[0572] The resin compositions obtained in each example were coated onto a 38 μm thick PET film (manufactured by Teijin Corporation, trade name: G2-38), and then heated and dried at 170°C for 5 minutes to produce a B-stage resin film. After peeling the resin film off the PET film, it was pulverized to obtain B-stage resin powder.

[0573] The resin powder obtained above was fed onto a Teflon (registered trademark) sheet cut to dimensions of 1 mm thickness × 50 mm length × 35 mm width. Low-profile copper foil (manufactured by Mitsui Metals & Mining Co., Ltd., trade name: 3EC-VLP-18) with a thickness of 18 μm was placed on both sides. It should be noted that the low-profile copper foil was arranged with the M-side facing the resin powder. Next, the laminate before heat and pressure forming was subjected to heat and pressure forming at a temperature of 230°C, a pressure of 2.0 MPa, and a time of 120 minutes to shape and cure the resin powder into a resin board, thereby producing a resin board with copper foil on both sides. The thickness of the resin board portion of the resulting resin board with copper foil on both sides is 1 mm.

[0574] [Measurement and Evaluation Methods]

[0575] Using the double-sided copper foil resin plates obtained in the above examples and comparative examples, various measurements and evaluations were performed according to the following methods. The results are shown in Table 2.

[0576] (1. Methods for determining the relative permittivity and dielectric loss tangent of cured materials)

[0577] The resin plates with copper foil on both sides obtained in each example were immersed in a 10% by mass solution of ammonium persulfate (manufactured by MITSUBISHI GAS CHEMICAL Co., Ltd.) as a copper etching solution to remove the copper foil and prepare a 2 mm × 50 mm test piece. Next, the relative permittivity (Dk) and dielectric loss tangent (Df) of the above test piece were measured according to the cavity resonator perturbation method at an ambient temperature of 25°C and a frequency band of 10 GHz.

[0578] (2. Method for determining peel strength)

[0579] The copper foil on both sides of the resin board obtained in each example was etched into a straight line 5 mm wide, and then dried at 105°C for 1 hour. The resulting material was used as a test piece. Next, according to JIS C6481:1996, the straight copper foil formed on the test piece was peeled off at a 90° angle, thereby measuring the peel strength of the copper foil. It should be noted that the measurement was performed using the "EZ-Test / CE" instrument manufactured by Shimadzu Corporation, and the tensile speed during copper foil peeling was 50 mm / min.

[0580] [Table 2]

[0581] Table 2

[0582]

[0583] It should be noted that the details of each component shown in Table 2 are as follows.

[0584] [(A) ingredient]

[0585] • Aromatic bismaleimide compounds containing indane rings: number average molecular weight = 1,300

[0586] [(A')Component]

[0587] • Biphenyl aralkyl maleimide compounds: trade name "MIR-3000" (manufactured by Nippon Kayaku Co., Ltd.)

[0588] [(B) Component]

[0589] <(B1) component>

[0590] • Conjugated diene polymer: 1,2-polybutadiene homopolymer, number average molecular weight = 1,200, vinyl content = ≥ 85%, tensile modulus of elasticity at 25°C = 0.05 GPa

[0591] <(B2) component>

[0592] • Modified conjugated diene polymer 1: The modified conjugated diene polymer 1 obtained in Manufacturing Example 1 has a tensile modulus of elasticity of 0.1 GPa at 25°C.

[0593] • Modified conjugated diene polymer 2: The modified conjugated diene polymer 2 obtained in Manufacturing Example 2 has a tensile modulus of elasticity of 0.1 GPa at 25°C.

[0594] <(B3) Ingredient>

[0595] • Styrene-based elastomer: Trade name "Tuftec (registered trademark) H1221" (manufactured by Asahi Kasei Corporation), hydrogenated styrene-based thermoplastic elastomer (SEBS; styrene-ethylene-butene-styrene copolymer), styrene content = 12% by mass, MFR = 4.5 g / 10 min under the test conditions of 230°C and 2.16 kgf load, number average molecular weight = 170,000, tensile modulus of elasticity at 25°C = 0.5 GPa

[0596] <(B4) component>

[0597] • Polyphenylene ether resin: Trade name "S203A" (manufactured by Asahi Kasei Corporation), number average molecular weight = 12,000, average number of phenolic hydroxyl groups per molecule = 1.8, tensile modulus of elasticity at 25°C = 2.2 GPa

[0598] <(B5) Ingredients>

[0599] • Organosilicon resin: Trade name "X-22-9412" (manufactured by Shin-Etsu Chemical Co., Ltd.), a vinyl polysiloxane diamine, with a reactive group equivalent of 430 g / mol and a tensile modulus of elasticity at 25°C of 0.1 GPa.

[0600] <(B6) Ingredients>

[0601] • Epoxy resin: Trade name "HP-7200H" (DIC Corporation), dicyclopentadiene type epoxy resin (epoxy resin with an alicyclic backbone), tensile modulus of elasticity at 25°C = 2.8 GPa

[0602] According to Table 2, the resin compositions obtained in Examples 1 to 8 of this embodiment have low relative permittivity and dielectric loss tangent, resulting in high peel strength. This indicates that the resin compositions of this embodiment exhibit excellent dielectric properties and conductor adhesion in high-frequency bands above 10 GHz. On the other hand, the resin compositions obtained in Comparative Examples 1 to 3 have a poor relative permittivity, dielectric loss tangent, and peel strength, resulting in insufficient balance between dielectric properties and conductor adhesion.

[0603] Industrial availability

[0604] The cured product made from the resin composition of this embodiment exhibits excellent dielectric properties and conductor adhesion in high-frequency bands above 10 GHz. Therefore, the resin composition of this embodiment is useful for fifth-generation mobile communication system (5G) antennas using radio waves exceeding 6 GHz, and printed circuit boards used in millimeter-wave radars using radio waves in the 30-300 GHz band.

Claims

1. A resin composition comprising: (A) Selected from one or more aromatic maleimide compounds and their derivatives, wherein the aromatic maleimide compound comprises a fused ring of an aromatic ring and an aliphatic ring in its molecular structure and has two or more N-substituted maleimide groups; and (B) Resins with a tensile modulus of elasticity of less than 10 GPa at 25°C. The condensed ring is an indene ring. The resin with a tensile modulus of elasticity of 10 GPa or less at 25°C, as described in (B), is selected from one or more of the following: ① to ⑤. ① A modified conjugated diene polymer obtained by modifying (b1) a conjugated diene polymer having vinyl groups on its side chain with (b2) a maleimide compound having two or more N-substituted maleimide groups, wherein (b2) is a maleimide compound having two or more N-substituted maleimide groups in a fused ring structure containing aromatic and aliphatic rings in its molecular structure; ② Conjugated diene polymers with a number-average molecular weight of 400–3000 and vinyl groups in the side chain; ③ SEBS is a hydride of styrene-butadiene-styrene block copolymer containing 5% to 20% by mass of styrene structural units. ④ Polyphenylene ether resin; ⑤ Organosilicon resins.

2. The resin composition according to claim 1, wherein, The indene ring is included in component (A) as a divalent group represented by the following general formula (a1-1). In the formula, R a1 The carbon atoms are alkyl (1-10), alkoxy (1-10), alkylthio (1-10), aryl (6-10), aryloxy (6-10), arylthio (6-10), arylthio (6-10), cycloalkyl (3-10), halogen atoms, hydroxyl or mercapto groups, n1 is an integer from 0 to 3, and R a2 ~R a4 Each is an alkyl group having 1 to 10 carbon atoms; * indicates a bonding site.

3. A prepreg containing the resin composition of claim 1 or 2 or a semi-cured product of the resin composition.

4. A laminate comprising a cured resin composition of claim 1 or 2 or a cured prepreg of claim 3 and a metal foil.

5. A resin film comprising the resin composition of claim 1 or 2 or a semi-cured product of the resin composition.

6. A printed circuit board having one or more of the following: a cured resin composition of claim 1 or 2, a cured prepreg of claim 3, and a laminate of claim 4.

7. A semiconductor package having the printed circuit board and semiconductor element as described in claim 6.

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