Conjugated diene-based copolymer, conjugated diene-based copolymer composition, resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit substrate

Abstract

A conjugated diene-based copolymer satisfying the following conditions (1) to (3). (Condition (1)) having: a polymer block (A) containing a vinyl aromatic monomer unit (a-1) having a radical-reactive group; a polymer block (B) mainly composed of a conjugated diene monomer unit (b); and a random polymer block (C) containing the above-mentioned vinyl aromatic monomer unit (a-1) having a radical-reactive group and the above-mentioned conjugated diene monomer unit (b), and mainly composed of the total of the above-mentioned vinyl aromatic monomer unit (a) containing the above-mentioned unit (a-1) and the above-mentioned conjugated diene monomer unit (b). (Condition (2)) having a number average molecular weight of more than 40,000 and 150,000 or less. (Condition (3)) having a content of the total of the vinyl aromatic monomer units (a) containing the above-mentioned unit (a-1) in the above-mentioned conjugated diene-based copolymer of 5 to 70 mass%.

Description

Technical Field

[0001] This invention relates to conjugated diene copolymers, conjugated diene copolymer compositions, resin compositions, cured products, resin films, prepregs, laminates, and materials for electronic circuit boards. Background Technology

[0002] In recent years, with the significant advancements in information network technology and the expansion of services utilizing information networks, there is a growing demand for electronic devices to achieve larger information capacities and higher processing speeds. To meet these requirements, materials with low dielectric loss are being sought for insulating layers on various substrates, such as printed circuit boards and flexible substrates.

[0003] In order to obtain materials with low dielectric loss, research and publication have been conducted on resin cured products with free radical curing thermosetting resins, such as polyphenylene ether resins with low dielectric constant and / or low dielectric loss tangent and excellent mechanical properties such as strength, as the main components.

[0004] However, previously disclosed materials still have room for improvement in terms of low dielectric constant and low dielectric loss tangent, resulting in limitations on information capacity and processing speed when used on printed circuit boards. Furthermore, to reduce transmission loss, low-roughness copper foil is used as the conductor. While using low-roughness copper foil reduces transmission loss, it also leads to a decrease in adhesion to the aforementioned insulating layer.

[0005] In order to improve this problem, various rubber components have been proposed as modifiers for thermosetting resins like the one described above.

[0006] For example, Patent Document 1 discloses at least one elastomer selected from the group consisting of block copolymers of vinyl aromatic compounds and olefinic olefin compounds and their hydrides, and homopolymers of vinyl aromatic compounds, as a modifier for achieving low dielectric loss tangent and low dielectric constant of polyphenylene ether resin.

[0007] In addition, in Patent Document 2, a styrene-based elastomer is disclosed as a modifier for achieving low dielectric loss tangent and low dielectric constant of epoxy resin.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2021-147486

[0011] Patent Document 2: Japanese Patent Application Publication No. 2020-15861 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] However, resin compositions using the modifiers disclosed in Patent Documents 1 and 2 still suffer from insufficient balance between low dielectric constant, low dielectric loss tangent, heat resistance, and adhesion to metal foils. In view of the above problems, techniques are known to increase the amount of rubber component to improve low dielectric constant, low dielectric loss tangent, and adhesion to metal foils, but these techniques result in thickening during curing.

[0014] Therefore, the object of the present invention is to provide a conjugated diene copolymer that yields a cured product with a low dielectric constant and a low dielectric loss tangent, as well as excellent heat resistance and adhesion to metal foil, and a resin composition containing the above-mentioned conjugated diene copolymer.

[0015] Methods for solving problems

[0016] In order to solve the problems of the prior art, the inventors conducted in-depth research and found that the cured product of the resin composition containing the conjugated diene copolymer with a specified structure has a low dielectric constant and a low dielectric loss tangent, and also has excellent heat resistance, thus completing the present invention.

[0017] That is, the present invention is as follows. [1]

[0019] A conjugated diene copolymer that satisfies the following conditions (1) to (3).

[0020] (Condition (1))

[0021] have: Polymer blocks (A) containing vinyl aromatic monomer units (a-1) with free radical reactive groups, Polymer blocks (B) mainly composed of conjugated diene monomer units (b), and A random polymer block (C) comprising the vinyl aromatic monomer unit (a-1) having the above-mentioned free radical reactive group and the above-mentioned conjugated diene monomer unit (b), and the main body being the sum of the vinyl aromatic monomer unit (a) comprising the above-mentioned unit (a-1) and the above-mentioned conjugated diene monomer unit (b).

[0022] (Condition (2))

[0023] The number-average molecular weight of the above-mentioned conjugated diene copolymers exceeds 40,000 but is less than 150,000.

[0024] (Condition (3))

[0025] The content of all vinyl aromatic monomer units (a) containing the above-mentioned unit (a-1) in the above-mentioned conjugated diene copolymer is 5 to 70% by mass. [2]

[0027] According to the conjugated diene copolymer described above [1], the conjugated diene copolymer also satisfies the following condition (4).

[0028] (Condition (4))

[0029] The number-average molecular weight of the above-mentioned conjugated diene copolymers exceeds 40,000 but is less than 100,000. [3]

[0031] According to the conjugated diene copolymer described in [1] or [2] above, wherein the polymer block (A) further comprises vinyl aromatic monomer units (unit (a-2)) (excluding unit (a-1)), The polymer block (A) described above is mainly composed of the vinyl aromatic monomer unit (a-1) and the vinyl aromatic monomer unit (a-2) described above, which have free radical reactive groups. The total content of the above-mentioned units (a-1) and (a-2) in the above-mentioned conjugated diene copolymer is 5% to 70% by mass. The random polymer block (C) further comprises a vinyl aromatic monomer unit (unit (a-2)) (excluding unit (a-1)), and the random polymer block (C) is mainly composed of the sum of the unit (a-1), the unit (a-2) and the conjugated diene monomer unit (b). [4]

[0033] The conjugated diene copolymer according to any one of [1] to [3] above, wherein the conjugated diene monomer unit (b) is a non-cyclic conjugated diene monomer unit. [5]

[0035] The conjugated diene copolymer according to any one of [1] to [4] above, wherein at least a portion of the conjugated diene monomer units of the conjugated diene copolymer are hydrogenated. [6]

[0037] The conjugated diene copolymer according to any one of [3] to [5] above, wherein the conjugated diene copolymer also satisfies the following condition (5).

[0038] (Condition (5))

[0039] The mass ratio of the above unit (a-1) to the above unit (a-2) is (a-1) / (a-2) = 30 / 70 to 99 / 1. [7]

[0041] The conjugated diene copolymer according to any one of [1] to [6] above, wherein at least a portion of the conjugated diene monomer units of the conjugated diene copolymer are hydrogenated at a hydrogenation rate of 98% or less. [8]

[0043] According to any one of [1] to [7] above, the conjugated diene copolymer, wherein at least a portion of the conjugated diene monomer unit of the conjugated diene copolymer is hydrogenated, and the hydrogenation rate is 50% or more and 98% or less. [9]

[0045] The conjugated diene copolymer according to any one of [1] to [8] above, wherein the conjugated diene copolymer has three or more ends.

[10]

[0047] The conjugated diene copolymer according to any one of [1] to [9] above, wherein the conjugated diene copolymer has 5 or more ends.

[11]

[0049] A conjugated diene copolymer composition comprising: The conjugated diene copolymer (conjugated diene copolymer (D)) described above [1]; and Conjugated diene copolymers (E) that satisfy the following conditions (6) to (7)

[0050] (Condition (6))

[0051] The number average molecular weight is below 40,000.

[0052] (Condition (7))

[0053] The polymer block comprises at least one polymer block selected from the group consisting of polymer block (A), random polymer block (C), and polymer block (B), and has polymer block (A) and / or random polymer block (C), wherein polymer block (A) comprises a vinyl aromatic monomer unit (a-1) having a free radical reactive group, wherein random polymer block (C) comprises the unit (a-1) and a conjugated diene monomer unit (b), and is mainly composed of the total of the vinyl aromatic monomer unit (a) comprising the unit (a-1) and the conjugated diene monomer unit (b), and wherein polymer block (B) is mainly composed of a conjugated diene monomer unit.

[12]

[0055] According to the conjugated diene copolymer composition described above

[11] , wherein the polymer block (A) constituting the conjugated diene copolymer (E) further comprises vinyl aromatic monomer units (unit (a-2)) (excluding unit (a-1)), The polymer blocks (A) constituting the conjugated diene copolymer (E) are mainly composed of the vinyl aromatic monomer units (a-1) and (a-2) having free radical reactive groups. The random polymer block (C) constituting the conjugated diene copolymer (E) further comprises vinyl aromatic monomer units (unit (a-2)) (excluding unit (a-1)).

[13]

[0057] According to the conjugated diene copolymer composition described in

[11] or

[12] above, wherein the conjugated diene copolymer (E) also satisfies the following (condition (8)).

[0058] (Condition (8))

[0059] The ratio of the number-average molecular weight (MnD) of the above-mentioned conjugated diene copolymer (D) to the number-average molecular weight (MnE) of the above-mentioned conjugated diene copolymer (E) (MnD / MnE) is greater than 2.

[14]

[0061] A resin composition comprising: Component (I): any one of the conjugated diene copolymers described in [1] to

[10] above, or any one of the conjugated diene copolymer compositions described in

[11] to

[13] above; and Select at least one component from the group consisting of components (II) to (III) below.

[0062] Component (II): Free radical initiator; Component (III): Curing resin (excluding component (I))

[15] According to the resin composition described above

[14] , wherein the above component (III) is a free radical curable resin and is a curable resin having at least one reactive group selected from the group consisting of vinyl, maleimide, allyl and methacryloyl as a reactive group.

[16]

[0064] The cured product of the conjugated diene copolymer described in any one of [1] to

[10] above.

[17]

[0066] The cured product of the conjugated diene copolymer composition described in any one of

[11] to

[13] above.

[18]

[0068] The cured product of the resin composition described above

[14] .

[19]

[0070] A resin film comprising the resin composition described above

[14] .

[20]

[0072] A prepreg, which is a composite of a substrate and the resin composition described above

[14] . [twenty one]

[0074] According to the prepreg described above

[20] , the substrate is glass cloth. [twenty two]

[0076] A laminate having the resin film and metal foil described above

[19] . [twenty three]

[0078] A material for electronic circuit boards comprising the cured material described above

[18] . [twenty four]

[0080] A material for an electronic circuit board comprising the resin film described above

[19] .

[25]

[0082] A material for an electronic circuit board comprising the prepreg described above

[20] .

[0083] The effects of the invention

[0084] According to the present invention, a conjugated diene copolymer having a low dielectric constant and low dielectric loss tangent, as well as excellent heat resistance and adhesion to metal foil, and a resin composition containing the above-mentioned conjugated diene copolymer can be provided. Detailed Implementation

[0085] The specific embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail below.

[0086] It should be noted that the following embodiments are illustrative of the present invention and are not intended to limit the present invention to the following content. The present invention can be implemented in various modifications within the scope of its essential points.

[0087] [Conjugated diene copolymer]

[0088] The conjugated diene copolymer of this embodiment is a conjugated diene copolymer that satisfies the following conditions (1) to (3).

[0089] (Condition (1))

[0090] have: Polymer blocks (A) containing vinyl aromatic monomer units (a-1) with free radical reactive groups, Polymer blocks (B) mainly composed of conjugated diene monomer units (b), and A random polymer block (C) comprising the vinyl aromatic monomer unit (a-1) having the above-mentioned free radical reactive group and the above-mentioned conjugated diene monomer unit (b), and the main body being the sum of the vinyl aromatic monomer unit (a) comprising the above-mentioned unit (a-1) and the above-mentioned conjugated diene monomer unit (b).

[0091] (Condition (2))

[0092] The number-average molecular weight of the above-mentioned conjugated diene copolymers exceeds 40,000 but is less than 150,000.

[0093] (Condition (3))

[0094] The content of all vinyl aromatic monomer units (a) containing the above-mentioned unit (a-1) in the above-mentioned conjugated diene copolymer is 5 to 70% by mass.

[0095] According to the conjugated diene copolymer of this embodiment, a cured product with low dielectric constant and low dielectric loss tangent and excellent heat resistance can be obtained.

[0096] (Condition (1))

[0097] The conjugated diene copolymer of this embodiment has a polymer block (A) containing a vinyl aromatic monomer unit (a-1) having a free radical reactive group (hereinafter sometimes referred to as unit (a-1)).

[0098] It should be noted that the polymer block (A) is mainly composed of vinyl aromatic monomer units.

[0099] That is, the polymer block (A) may be based on the above-described unit (a-1), or it may contain the above-described unit (a-1) and vinyl aromatic monomer units (a-2) other than (a-1), with their total being the main component. In this specification, the unit (a) is sometimes referred to as the collective term for the vinyl aromatic monomer units in the polymer block (A).

[0100] Here, "as the main component" means that the amount of vinyl aromatic monomer units in the polymer block (A) is 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and more preferably 100% by mass (without actively including other copolymer components).

[0101] From the perspective of reactivity, as described later, the content of the aforementioned unit (a-1) in the polymer block (A) is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and even more preferably 85% by mass or more.

[0102] The vinyl aromatic monomer unit (a-1) has a radical reactive group.

[0103] A vinyl aromatic monomer unit with a free radical reactive group refers to a structural unit derived from a vinyl aromatic compound that is reactive with free radicals, generated by the polymerization of such compounds.

[0104] "Free radical reactive groups" refer to chemical groups that can generate free radicals and / or induce the formation of free radicals through the action of heat and / or light and / or free radical initiators.

[0105] By incorporating the conjugated diene copolymer of this embodiment with a vinyl aromatic monomer unit (a-1) having a free radical reactive group, the cured resin composition using the conjugated diene copolymer of this embodiment tends to have excellent heat resistance.

[0106] There are no particular limitations on free radical reactive groups as long as they can generate free radicals. They can be any chemical group, as long as they exist as a functional group with free radical reactivity in the conjugated diene copolymer after the monomer is polymerized (and are not consumed during polymerization to maintain free radical reactivity).

[0107] The free radical reactive groups mentioned above are not limited to the examples listed below. For example, chemical groups that generate free radicals mainly through light and / or free radical initiators can include benzophenone group, benzoyl group, groups containing anthraquinone skeleton, and thioxanthone group.

[0108] In addition, examples of chemical groups that generate free radicals through heat and / or light and / or free radical initiators include groups containing disulfide bonds and groups containing peroxide bonds. Examples of chemical groups that generate free radicals mainly through heat and / or free radical initiators include benzyl carbon having at least one hydrogen substituent, mercapto, vinyl, groups containing an alkoxyamine skeleton, and groups containing an azo bond.

[0109] Furthermore, even if the chemical groups exemplified above have other substituents or are bonded to other atomic groups, as long as free radical species can be generated, from the perspective of the dielectric properties of the cured resin composition using the conjugated diene copolymer of this embodiment, it is preferable to have low polarity chemical groups containing benzyl carbon having at least one hydrogen substituent or chemical groups containing vinyl groups.

[0110] As a vinyl aromatic monomer having a free radical reactive group that forms a vinyl aromatic monomer unit (a-1) having a free radical reactive group, examples of which include, but are not limited to, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, o-isopropylstyrene, p-isopropylstyrene, o-methyl-α-methylstyrene, p-methyl-α-methylstyrene, o-ethyl-α-methylstyrene, p-ethyl-α-methylstyrene, o-isopropyl-α-methylstyrene, p-isopropyl-α-methylstyrene, divinylbenzene, or any mixture thereof, are preferred from the above-mentioned reactivity aspect.

[0111] They can be used individually or in combination of two or more.

[0112] The polymer block (A) constituting the conjugated diene copolymer of this embodiment may contain a vinyl aromatic monomer unit (a-2) (excluding the unit (a-1) mentioned above. Hereinafter referred to as unit (a-2)).

[0113] In this case, the polymer block (A) is mainly composed of a vinyl aromatic monomer unit (a) that combines the vinyl aromatic monomer unit (a-1) with the vinyl aromatic monomer unit (a-2) having free radical reactive groups.

[0114] Here, "mainly composed of vinyl aromatic monomer units (a-1) and vinyl aromatic monomer units (a-2) (excluding (a-1)) having free radical reactive groups" means that the total mass of the above-mentioned units (a-1) and (a-2) in the above-mentioned polymer block (A) is 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and more preferably 100% by mass (without actively including other copolymer components).

[0115] Furthermore, when the conjugated diene copolymer of this embodiment includes the above-described unit (a-1) and unit (a-2), the units (a-1) and (a-2) in the polymer block (A) can be uniformly distributed or distributed in a gradient manner. Additionally, there can be a plurality of uniformly distributed portions and / or gradient-distributed portions of the units (a-1) and (a-2).

[0116] The vinyl aromatic monomer unit (a-2) refers to the structural unit derived from vinyl aromatic compounds in copolymers formed by the polymerization of vinyl aromatic compounds.

[0117] Examples of vinyl aromatic compounds that form the above-mentioned unit (a-2) include, but are not limited to, styrene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc.

[0118] These substances can be used alone or in combination of two or more.

[0119] By incorporating polymer blocks (A) containing the aforementioned unit (a-1) into the conjugated diene copolymer of this embodiment, the conjugated diene copolymer of this embodiment exhibits reactivity with component (III) described later: the curable resin. This enables the resin composition of this embodiment to achieve a low dielectric loss tangent, a low dielectric constant, and improved heat resistance. Furthermore, by having the aforementioned unit (a-2) in the polymer block (A), the reactivity of the conjugated diene copolymer of this embodiment with component (III) described later: the curable resin can be appropriately controlled.

[0120] The conjugated diene copolymer of this embodiment has polymer blocks (B) mainly composed of conjugated diene monomer units (unit (b)) (hereinafter sometimes referred to as polymer blocks (B)).

[0121] Here, "mainly composed of conjugated diene monomer unit (b)" means that the total amount of the above-mentioned unit (b) in the above-mentioned polymer block (B) is 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and even more preferably 100% by mass (without actively including other copolymer components).

[0122] The conjugated diene monomer unit (b) refers to the structural unit derived from the conjugated diene compound in the conjugated diene copolymer formed by the polymerization of conjugated diene compounds.

[0123] The conjugated diene compound is a diene having a pair of conjugated double bonds, preferably acyclic. That is, the conjugated diene monomer unit (b) is preferably acyclic conjugated diene monomer unit. By making the conjugated diene monomer unit (b) acyclic conjugated diene monomer unit, the flexibility of the conjugated diene copolymer of this embodiment tends to be improved, and the adhesion to the metal foil tends to be improved.

[0124] Examples of conjugated diene compounds include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, isoprene, etc., or mixtures thereof. From the perspective of availability, 1,3-butadiene, 2-methyl-1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, and more preferably 1,3-butadiene.

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

[0126] In addition, the aforementioned conjugated diene compounds can also be biologically derived conjugated diene compounds.

[0127] By incorporating the conjugated diene copolymer of this embodiment with the aforementioned polymer block (B), the conjugated diene copolymer of this embodiment is softened, and the resin composition of this embodiment and the cured product formed from the resin composition, described later, are softened, tending to have improved adhesion to metal foil.

[0128] The conjugated diene copolymer of this embodiment has a random polymer block (C) comprising the vinyl aromatic monomer unit (a-1) having the above-mentioned free radical reactive group and the conjugated diene monomer unit (unit (b)).

[0129] The random polymer block (C) is mainly composed of the vinyl aromatic monomer unit (a) containing the above-mentioned unit (a-1) and the above-mentioned conjugated diene monomer unit (b).

[0130] The random polymer block (C) may further include a vinyl aromatic monomer unit (unit (a-2)) (excluding unit (a-1)), in which case the random polymer block (C) is mainly composed of the sum of the unit (a-1), the unit (a-2) and the conjugated diene monomer unit (b).

[0131] Here, "mainly consisting of vinyl aromatic monomer units (a-1) containing vinyl aromatic monomer units with free radical reactive groups and the aforementioned conjugated diene monomer units" means that the total amount of the aforementioned unit (a-1) and the aforementioned unit (b) in the aforementioned polymer block (C), or the total amount of the aforementioned unit (a-1), the aforementioned unit (a-2), and the aforementioned unit (b) is 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further more preferably 95% by mass or more, and even more preferably 100% by mass (without actively including other copolymer components).

[0132] The polymer block (B) primarily composed of conjugated diene monomer units (b) tends to have lower compatibility with the curable resin described later (III) compared to the polymer block (A) and the random polymer block (C) containing the aforementioned unit (a-1) and optionally the aforementioned unit (a-2). Therefore, it tends to have reduced heat resistance due to the difficulty in forming bonds with the later-described component (III). Thus, the conjugated diene copolymer of this embodiment, by having the random polymer block (C) containing the aforementioned unit (b) and the aforementioned unit (a-1), and optionally the aforementioned unit (a-2), tends to achieve a balance between the aforementioned softness and reactivity with component (III). From the perspective of balancing softness and reactivity, the random polymer block (C) has the aforementioned unit (a-1) and the aforementioned conjugated diene monomer units (b), and optionally has unit (a-2).

[0133] There are no particular limitations on the distribution of the aforementioned unit (a-1) and the optionally included unit (a-2) in the polymer block (C). Units (a-1) and (a-2) can be uniformly distributed or distributed in a gradient manner in the random polymer block (C). In addition, there can be multiple portions of uniformly distributed units (a-1) and / or gradient-distributed units (a-2), and there can also be multiple segments with different contents of vinyl aromatic monomer units (a).

[0134] Regarding the macroscopic structure described above, the composition ratio of the vinyl aromatic monomer unit (a-1) having a free radical reactive group, the vinyl aromatic monomer unit (a-2) excluding (a-1), and the conjugated diene monomer unit (b) in the conjugated diene copolymer of this embodiment, the unhydrogenated conjugated diene copolymer or the hydrogenated conjugated diene copolymer can be used as the analyte and determined by using a nuclear magnetic resonance (NMR) method (the method described in Y. Tanaka, et al., RUBBERCHEMISTRY and TECHNOLOGY 54,685 (1981), hereinafter referred to as "NMR method").

[0135] (Condition (2), Condition (4))

[0136] The number-average molecular weight of the conjugated diene copolymer in this embodiment is greater than 40,000 and less than 150,000.

[0137] The number-average molecular weight was determined as follows: based on a calibration curve derived from the determination of commercially available standard polystyrene (using the peak molecular weight of the standard polystyrene), the peak molecular weight of the chromatogram obtained by gel permeation chromatography (GPC) was measured, and the number-average molecular weight was thus determined. Specifically, it can be determined by the method described in the examples below.

[0138] The resin films, prepregs, laminates, and electronic circuit board materials comprising the aforementioned resin films, prepregs, or laminates are typically manufactured by dissolving each material in an organic solvent and then mixing and molding them. Therefore, from the perspective of solubility in organic solvents, the number-average molecular weight of the conjugated diene copolymer of this embodiment is 150,000 or less, preferably 130,000 or less, and more preferably 100,000 or less. From the perspective of processability of the conjugated diene copolymer of this embodiment, the lower limit of the number-average molecular weight is more than 40,000, preferably 45,000 or more, and more preferably 50,000 or more. By making the number-average molecular weight exceed 40,000, it is possible to prevent the conjugated diene copolymers from sticking together thermally, thus tending to obtain good processability.

[0139] The number-average molecular weight of the conjugated diene copolymer in this embodiment can be controlled within the above-mentioned range by adjusting polymerization conditions such as monomer addition amount, addition timing, polymerization temperature, and polymerization time.

[0140] (Condition (3))

[0141] In the conjugated diene copolymer of this embodiment, the content of all vinyl aromatic monomer units (a) containing the vinyl aromatic monomer unit (a-1) having the free radical reactive group in the conjugated diene copolymer is 5 to 70% by mass.

[0142] Furthermore, in the case where the conjugated diene polymer block of this embodiment contains a vinyl aromatic monomer unit (a-2) (excluding unit (a-1)), since the vinyl aromatic monomer unit (a-2) is a vinyl aromatic monomer unit other than the vinyl aromatic monomer unit (a-1) with a free radical reactive group, the total mass of the above-mentioned unit (a-1) and the above-mentioned unit (a-2) in the conjugated diene copolymer of this embodiment is 5 to 70 by mass.

[0143] As described above, from the perspective of SP value, the compatibility with component (III) described later tends to be that the above-described units (a-1) and (a-2) are superior to the above-described conjugated diene monomer unit (b). In contrast, by having the above-described conjugated diene monomer unit (b), the conjugated diene copolymer of this embodiment is softened and tends to have improved adhesion to metal foil. Therefore, from the perspective of balancing the above-described compatibility and the above-described adhesion, the content of all vinyl aromatic monomer units including the above-described unit (a-1) in the conjugated diene copolymer of this embodiment, or the total amount of the above-described units (a-1) and the above-described units (a-2), is 5 to 70% by mass, preferably 10 to 70% by mass, more preferably 15 to 70% by mass, further preferably 20 to 70% by mass, further more preferably 25 to 70% by mass, even more preferably 25 to 65% by mass, particularly preferably 25 to 60% by mass, and most preferably 25 to 55% by mass.

[0144] The content of unit (a-1) and unit (a-2) in the conjugated diene copolymer of this embodiment can be controlled within the above-mentioned numerical range by adjusting the type, amount, timing of addition, and polymerization time of the monomer in the polymerization process.

[0145] Furthermore, from the perspective of the reactivity of the conjugated diene copolymer of this embodiment with the component (III) described later, the mass ratio of the above-mentioned unit (a-1) to the above-mentioned unit (a-2) of the conjugated diene copolymer of this embodiment is preferably (a-1) / (a-2) = 30 / 70 to 100 / 0.

[0146] It should be noted that when (a-1) / (a-2)=100 / 0, it means that the element (a-2) is not included.

[0147] When the above-mentioned unit (a-2) is included, the lower limit value of (a-1) / (a-2) is more preferably 50 / 50 or more, further preferably 60 / 40 or more, even more preferably 70 / 30 or more, even more preferably 80 / 20 or more, particularly preferably 90 / 10 or more, even more preferably 95 / 5 or more, even more preferably 98 / 2, and most preferably 99 / 1 or more.

[0148] Furthermore, when unit (a-2) is included, the upper limit of (a-1) / (a-2) is more preferably 99 / 1 or less.

[0149] By making the sum of the above-mentioned unit (a-1) and the above-mentioned unit (a-2) 30% by mass or more and 99% by mass or less (condition (5)), the conjugated diene copolymer of this embodiment has sufficient reactivity and tends to have low dielectric loss tangent, low dielectric constant and improved heat resistance of the resin composition of this embodiment, which will be described later.

[0150] (Hydrogenation rate)

[0151] As described above, the conjugated diene copolymer of this embodiment has polymer blocks (B) mainly composed of conjugated diene monomer units (b). Additionally, it has random polymer blocks (C) composed of conjugated diene monomer units (b).

[0152] In the conjugated diene copolymer of this embodiment, at least a portion of the conjugated diene monomer unit (b) is hydrogenated.

[0153] Recently, in order to reduce scattering losses in various electronic devices, the metal foils used in conductors, especially copper foils, tend to use low-roughness copper foils. Therefore, it is required that the insulating layer has high adhesion to low-roughness metal foils.

[0154] It is known that the conjugated diene copolymer of this embodiment has aliphatic double bonds based on conjugated diene monomer units, which have higher radical reactivity than the vinyl aromatic monomer units (a-1) with radical reactive groups described above. Therefore, by generating bonds with component (III) described later: the curable resin, and bonds between the conjugated diene copolymers, a cured product with high crosslinking density can be obtained, which tends to have CTE optimization.

[0155] On the other hand, due to the decrease in molecular weight between crosslinking points, the cured material becomes rigid and tends to have reduced adhesion to the metal foil. Therefore, from the perspective of balancing the above-mentioned CTE and adhesion to the metal foil, in order to control the reactivity based on the conjugated diene monomer unit, the double bond of the above-mentioned conjugated diene monomer unit (b) in the conjugated diene copolymer of this embodiment is preferably hydrogenated.

[0156] Specifically, the hydrogenation rate of the conjugated diene copolymer in this embodiment is preferably 50% or more, more preferably 60% or more, further preferably 70% or more, even more preferably 75% or more, even more preferably 80% or more, particularly preferably 83% or more, and most preferably 85% or more. From the perspective of the above-mentioned CTE, the upper limit is preferably 98% or less, more preferably 96% or less.

[0157] A hydrogenation catalyst can be used in the above hydrogenation reaction.

[0158] Examples of hydrogenation catalysts include, but are not limited to: (1) supported heterogeneous hydrogenation catalysts made by supporting metals such as Ni, Pt, Pd, and Ru on carbon, silicon oxide, aluminum oxide, diatomaceous earth, etc.; (2) so-called Ziegler-type hydrogenation catalysts using transition metal salts such as organic acid salts of Ni, Co, Fe, and Cr or acetylacetone salts and reducing agents such as organoaluminum; and (3) so-called homogeneous hydrogenation catalysts such as organometallic compounds of Ti, Ru, Rh, and Zr.

[0159] Specifically, the hydrogenation catalysts described in Japanese Patent Publication Nos. 42-8704, 43-6636, 63-4841, 1-37970, 1-53851, and 2-9041 may be used as hydrogenation catalysts.

[0160] Preferred hydrogenation catalysts include cyclopentadiene titanium compounds and / or reducing organometallic compounds.

[0161] As a cyclopentadiene titanium compound, the compound described in Japanese Patent Application Publication No. 8-109219 may be used.

[0162] Examples of cyclopentadiene titanium compounds include, but are not limited to, compounds containing at least one ligand with a (substituted) cyclopentadiene, indene, or fluorene skeleton, such as dicyclopentadiene titanium dichloride and monopentanemethylcyclopentadiene titanium trichloride. In cyclopentadiene titanium compounds, the aforementioned skeleton may comprise a single skeleton or a combination of two skeletons.

[0163] Examples of reducing organometallic compounds include, but are not limited to, organoalkali metal compounds such as organolithium, organomagnesium, organoaluminum, organoboron, and organozinc compounds. These substances can be used alone or in combination of two or more.

[0164] The hydrogenation rate described above can be controlled by adjusting the reaction temperature, reaction time, hydrogen supply, and catalyst amount in the hydrogenation method. Regarding the temperature during the hydrogenation reaction, it is preferably carried out at 55–200°C, more preferably at 60–170°C, and even more preferably at 65–160°C. Furthermore, the pressure of the hydrogen used in the hydrogenation reaction is 0.1–15 MPa, preferably 0.2–10 MPa, and more preferably 0.3–5 MPa. Additionally, the hydrogenation reaction time is typically 3 minutes to 10 hours, preferably 10 minutes to 5 hours.

[0165] Hydrogenation can be carried out using batch processes, continuous processes, or combinations thereof.

[0166] (Macroscopic structure of conjugated diene copolymers)

[0167] From the perspective of the reactivity and mobility of the above-described conjugated diene copolymer with the curable resin described later (III), the conjugated diene copolymer of this embodiment preferably has a tendency to have higher reactivity at the ends of the conjugated diene copolymer than at the interior. From the perspective of reactivity, the number of ends of the conjugated diene copolymer is preferably more, preferably 3 or more, more preferably 5 or more. With a greater number of ends, the amount of reaction with the curable resin described later (III) increases, and the heat resistance of the resin composition of this embodiment tends to be further improved. In addition, from the perspective of obtaining the above-described appropriate crosslinking density, when the number of ends is 3 or more, the hydrogenation rate of the conjugated diene copolymer of this embodiment is preferably 60% or more, more preferably 65% ​​or more, further preferably 70% or more, and even more preferably 75% or more.

[0168] In this embodiment, the number of ends of the conjugated diene copolymer can be controlled within the above-mentioned range by using a specified branching agent during the polymerization process.

[0169] [Conjugated diene copolymer composition]

[0170] The conjugated diene copolymer composition of this embodiment contains the conjugated diene copolymer of this embodiment and a conjugated diene copolymer (E) that satisfies the following conditions (6) to (7)).

[0171] In order to distinguish the conjugated diene copolymer of this embodiment from the above-mentioned conjugated diene copolymer (E), the conjugated diene copolymer of this embodiment is sometimes referred to as conjugated diene copolymer (D) in this specification.

[0172] Methods for manufacturing the above-mentioned conjugated diene copolymer compositions include: (1) a method of separately performing solution polymerization on each component that forms two or more peaks in the chromatogram obtained by GPC determination, and then mixing the solution containing the polymer; (2) a method of separately removing the solvent and catalyst from each component and then mixing them; (3) a method of adding a polymerization initiator in two stages during the polymerization reaction; (4) a method of stopping the reaction of a portion of the active ends by adding a molar amount of a modifier, coupling agent, or protic reagent such as an alcohol that reacts at the active ends relative to the active ends during the polymerization reaction; (5) a method of adding an equimolar amount of a modifier or protic reagent such as an alcohol that acts as a polymerization terminator to the active ends after the polymerization reaction, stopping the reaction of all active ends, and then adding a polymerization initiator and monomer back into the solution to carry out polymerization; and so on.

[0173] In the method described in (1) above, either the method of mixing the polymerization solutions of each component before hydrogenation and then carrying out the hydrogenation reaction, or the method of carrying out the hydrogenation reaction of each component separately and then mixing their respective solutions, can be used. In addition, the mixing ratio of each component can be controlled to the desired value by adjusting the concentration of their respective polymerization solutions and the mixing volume of the solutions.

[0174] In the method described in (3) above, the mixing ratio of each component can be controlled to the desired value by adjusting the feed rate of the vinyl aromatic compound and the conjugated diene compound, the amount of polymerization initiator added in the two stages, and the timing of the addition of the polymerization initiator in the second stage.

[0175] In the method described in (4) above, the mixing ratio and structure of each component can be arbitrarily controlled by adjusting the feed rate and composition of the vinyl aromatic compound and the conjugated diene compound, the amount of modifier or polymerization terminator added midway, and the timing of addition.

[0176] As described in (1), (3), (4) and (5) above, when components that form two or more peaks in the chromatogram obtained by GPC determination are mixed before desolventizing, the desolventizing and refining process can be carried out at a high rate.

[0177] The methods described in (3) and (4) above can simultaneously produce the component with the largest number average molecular weight (IX) and the component with the smallest number average molecular weight (IN). Compared with producing the component (IX) and the component (IN) separately, this reduces the number of production steps and thus improves production efficiency.

[0178] As the coupling agent used in (4) above, any known coupling agent can be used, without particular limitation.

[0179] Examples of difunctional coupling agents include, but are not limited to, alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, etc.; dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, dimethyldibromosilane, etc.; and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

[0180] In addition, as a multifunctional coupling agent with three or more functions, any existing known multifunctional coupling agents can be used without particular limitation.

[0181] Examples of multifunctional coupling agents with three or more functions include, but are not limited to, polyols with three or more members; epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane, and other polyepoxide compounds; and compounds with the general formula R4-nSiX. n (Here, R represents a hydrocarbon group with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer from 3 to 4) represents silicon halide compounds, such as methyltrichlorosilane, tert-butyltrichlorosilane, silicon tetrachloride, and their bromides; general formula R4-nSnX n (Here, R represents a hydrocarbon group with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer from 3 to 4.) The tin halide compounds represented are, for example, methyltin trichloride, tert-butyltin trichloride, tin tetrachloride, and other polyhalides. Additionally, dimethyl carbonate, diethyl carbonate, etc., can also be used.

[0182] (Condition (6))

[0183] The number average molecular weight is below 40,000.

[0184] (Condition (7))

[0185] The polymer block comprises at least one polymer block selected from the group consisting of polymer block (A), random polymer block (C), and polymer block (B), and has polymer block (A) and / or random polymer block (C), wherein polymer block (A) comprises a vinyl aromatic monomer unit (a-1) having a free radical reactive group, wherein random polymer block (C) comprises the unit (a-1) and a conjugated diene monomer unit (b), and is mainly composed of the total of the vinyl aromatic monomer unit (a) comprising the unit (a-1) and the conjugated diene monomer unit (b), and wherein polymer block (B) is mainly composed of a conjugated diene monomer unit.

[0186] Recently, miniaturization of electronic circuit boards and densification of wiring have been continuously studied. Therefore, in order to cover dense wiring with the insulating layer when the conductor layer and insulating layer are laminated and cured, it is preferable that the viscosity of the insulating layer during curing is low. From the above-mentioned aspect of low viscosity, the material of the insulating layer is preferably a conjugated diene copolymer composition comprising the above-mentioned conjugated diene copolymer (D) and the above-mentioned conjugated diene copolymer (E).

[0187] As described above (condition (6)), the number average molecular weight of the conjugated diene copolymer (E) is 40,000 or less. That is, its molecular weight is lower than that of the conjugated diene copolymer (D) described above. Therefore, by including the conjugated diene copolymer (E), the conjugated diene copolymer composition of this embodiment tends to have a low viscosity. From the perspective of low viscosity, the number average molecular weight of the conjugated diene copolymer (E) is 40,000 or less.

[0188] In addition, the ratio of the number average molecular weight (MnE) of the above-mentioned conjugated diene copolymer (E) to the number average molecular weight (MnD) of the above-mentioned conjugated diene copolymer (D) (MnD / MnE) is preferably greater than 2 (condition (8)), more preferably 2.3 or more, further preferably 2.5 or more, more preferably 2.7 or more, even more preferably 3.0 or more, and particularly preferably 3.3 or more.

[0189] Therefore, the conjugated diene copolymer composition of this embodiment tends to have low viscosity.

[0190] As described above, the number-average molecular weight (MnE) of the conjugated diene copolymer (E) is 40,000 or less, preferably 35,000 or less, and more preferably 30,000 or less. There is no particular limitation on the lower limit. When the number-average molecular weight decreases, the molecular weight between crosslinking points decreases when reacting with component (III) (described later): the curable resin, making it difficult to form an appropriate crosslinking density. Consequently, the effect of lowering the dielectric constant and / or lowering the dielectric loss tangent of the resin composition of this embodiment tends to decrease. From the perspective of lowering the dielectric constant and / or lowering the dielectric loss tangent, the number-average molecular weight of the conjugated diene copolymer (E) is preferably 0.20 million or more, more preferably 0.25 million or more, further preferably 0.30 million or more, and even more preferably 0.35 million or more.

[0191] As described above, from the perspective of reducing the viscosity of the conjugated diene copolymer composition of this embodiment, the molecular weight of the conjugated diene copolymer (E) is lower than that of the conjugated diene copolymer (D). Lower molecular weight molecules are more prone to molecular motion than higher molecular weight molecules; therefore, if they remain as unreacted components in the cured product, the effect of lowering the dielectric constant and / or lowering the dielectric loss tangent tends to be reduced. In view of the above, from the perspective of ensuring good reactivity between the conjugated diene copolymer (E) and / or with the conjugated diene copolymer (D) and / or with the component (III) described later: the curable resin, the conjugated diene copolymer (E) has the polymer block (A) and / or the random polymer block (C) comprising a vinyl aromatic monomer unit (a-1) having a free radical reactive group, optionally having the polymer block (B) (condition (7)).

[0192] By making the above-mentioned conjugated diene copolymer (E) have the above-mentioned polymer block (A) and / or the above-mentioned polymer block (C) containing the above-mentioned unit (a-1), the above-mentioned conjugated diene copolymer (E) has sufficient reactivity, and the proportion of low molecular weight body present in the cured product of this embodiment is reduced, so there is a tendency to achieve both viscosity during curing and low dielectric constant and low dielectric loss tangent.

[0193] From the perspectives of low dielectric constant, low dielectric loss tangent, adhesion to metal foil, and low viscosity, the mass ratio of the conjugated diene copolymer (D) to the conjugated diene copolymer (E) in the above-mentioned conjugated diene copolymer composition is preferably 50 / 50 to 90 / 10, more preferably 50 / 50 to 85 / 15, and even more preferably 50 / 50 to 80 / 20.

[0194] Furthermore, when the conjugated diene copolymer (E) has the above-mentioned polymer block (A) and / or the above-mentioned polymer block (C), and preferably the number average molecular weight of the above-mentioned conjugated diene copolymer (E) is 10,000 or more, more preferably 15,000 or more, and even more preferably 20,000 or more, it is preferable that the ratio of conjugated diene copolymer (D) to conjugated diene copolymer (E) is 30 / 70 to 80 / 20, and more preferably 35 / 65 to 75 / 25.

[0195] When the conjugated diene copolymer (E) does not contain the aforementioned polymer block (A) and / or the aforementioned polymer block (C), and the content of the aforementioned conjugated diene copolymer (E) in the conjugated diene copolymer composition exceeds 70% by weight, the conjugated diene copolymer has low reactivity with the component (III) described later. Therefore, it tends to have a lower dielectric constant and a lower dielectric loss tangent in the conjugated diene copolymer composition of this embodiment. In addition, when the number average molecular weight of the aforementioned conjugated diene copolymer (E) is 10,000 or less, and the content of the aforementioned conjugated diene copolymer (E) in the conjugated diene copolymer composition exceeds 70% by weight, it tends to have reduced flexibility of the cured product and reduced adhesion to the metal foil described later. That is, from the perspective of balancing low dielectric constant, low dielectric loss tangent, adhesion to metal foil, and low viscosity, the conjugated diene copolymer (E) in the conjugated diene copolymer composition has the above-mentioned polymer block (A) and / or the above-mentioned polymer block (C), and the number average molecular weight is 10,000 or more. The mass ratio of the above-mentioned conjugated diene copolymer (D) to the above-mentioned conjugated diene copolymer (E) in the conjugated diene copolymer composition is preferably 30 / 70 to 80 / 20.

[0196] In the aforementioned conjugated diene copolymer (E), the polymer block (A) constituting the conjugated diene copolymer (E) may further include, in addition to the vinyl aromatic monomer unit (a-1) having a free radical reactive group, a vinyl aromatic monomer unit (a-2) (excluding unit (a-1)). It should be noted that, in the above case, the polymer block (A) is primarily composed of the sum of the aforementioned units (a-1) and (a-2).

[0197] In addition, in the above-mentioned conjugated diene copolymer (E), the random polymer block (C) may further include a vinyl aromatic monomer unit (a-2) (excluding unit (a-1)) in addition to the vinyl aromatic monomer unit (a-1) having a free radical reactive group.

[0198] (Vinyl bond weight)

[0199] In the conjugated diene copolymer (D) and low molecular weight conjugated diene copolymer (E) of this embodiment, the conjugated diene monomer unit (b) may comprise units (b-1) (hereinafter sometimes referred to as unit (b-1)) from 1,2-bonded and / or 3,4-bonded and units (b-2) (hereinafter sometimes referred to as unit (b-2)) from 1,4-bonded and units (b-1) from 1,4-bonded and units (b-2) from 1,4-bonded and units (b-2) from 1,4-bonded and units (b-1 ...

[0200] The content of the aforementioned unit (b-1) can be controlled to the above-mentioned numerical range by using a modifier such as a polar compound during polymerization, and can be calculated using the method described in the examples below.

[0201] Examples of such regulators include, but are not limited to, tertiary amine compounds and ether compounds. Tertiary amine compounds are preferred.

[0202] Tertiary amine compounds are compounds represented by the general formula: R1R2R3N (where R1, R2, and R3 are hydrocarbon groups with 1 to 20 carbon atoms, or hydrocarbon groups having a tertiary amine).

[0203] Examples of tertiary amine compounds include, but are not limited to, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinylethane, trimethylaminoethylpiperazine, N,N,N',N”,N”-pentamethylethylenetriamine, and N,N'-dioctyl-p-phenylenediamine.

[0204] [Method for manufacturing conjugated diene copolymers]

[0205] The conjugated diene copolymer (D) and the low molecular weight conjugated diene copolymer (E) of this embodiment can be manufactured, for example, by active anionic polymerization using a polymerization initiator such as an organoalkali metal compound in a hydrocarbon solvent.

[0206] Examples of hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcycloheptane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and so on.

[0207] As polymerization initiators, examples include aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amino alkali metal compounds, which are generally known to have anionic polymerization activity for conjugated diene compounds and vinyl aromatic compounds.

[0208] Examples of alkali metals include lithium, sodium, and potassium.

[0209] Examples of organoalkali metal compounds include aliphatic and aromatic hydrocarbon lithium compounds with 1 to 20 carbon atoms, including compounds containing one lithium atom in one molecule, dilithium compounds, trilithium compounds, and tetralithium compounds containing multiple lithium atoms in one molecule.

[0210] Examples of organoalkali metal compounds include, but are not limited to, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, the reaction product of diisopropylbenzene and sec-butyllithium, and the reaction product of divinylbenzene and sec-butyllithium with a small amount of 1,3-butadiene. Additionally, alkyl lithiums containing siloxy groups, such as 1-(tert-butoxy)propyllithium disclosed in U.S. Patent 5,708,092 and lithium compounds containing one to several molecules of isoprene monomer inserted to improve their solubility, alkyl lithiums containing siloxy groups, such as 1-(tert-butyldimethylsiloxy)hexyllithium disclosed in British Patent 2,241,239, alkyl lithiums containing amino groups, and amino lithiums such as diisopropylamine lithium and hexamethyldisilazine lithium disclosed in U.S. Patent 5,527,753, can also be used.

[0211] As a method for polymerizing vinyl aromatic compounds and conjugated diene compounds using organoalkali metal compounds as polymerization initiators, existing known methods can be applied.

[0212] The polymerization method can be, for example, batch polymerization, continuous polymerization, or a combination thereof. Batch polymerization is suitable for obtaining homogeneous polymer blocks.

[0213] The polymerization temperature is preferably 0℃~180℃, more preferably 30℃~150℃.

[0214] The polymerization time varies depending on the conditions, but is usually within 48 hours, preferably 0.1 to 10 hours.

[0215] In addition, an inert gas atmosphere such as nitrogen is preferred as the atmosphere for the polymerization system.

[0216] Regarding the polymerization pressure, it is not particularly limited as long as it is set within a pressure range that can maintain the monomer and solvent in a liquid phase within the aforementioned temperature range. Furthermore, care should be taken to avoid introducing impurities such as water, oxygen, or carbon dioxide into the polymerization system that could deactivate the catalyst and active polymer.

[0217] In addition, at the end of the above polymerization process, a coupling agent with two or more functions can be added to carry out a coupling reaction. The coupling rate is preferably 40% or less, more preferably 30% or less, further preferably 20% or less, and even more preferably does not contain a coupling agent.

[0218] As a difunctional coupling agent, any existing known coupling agents can be used without particular limitation.

[0219] Examples of difunctional coupling agents include, but are not limited to, alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; dihalides such as dichloroethane, dibromoethane, dimethyldichlorosilane, and dimethyldibromosilane; and esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

[0220] In addition, as a multifunctional coupling agent with three or more functions, any existing known coupling agents can be used without particular limitation.

[0221] Examples of multifunctional coupling agents with three or more functions include polyols with three or more members; epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane, and other polycyclic epoxy compounds; and compounds with the general formula R4-nSiX. n (Here, R represents a hydrocarbon group with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer from 3 to 4) represents silicon halide compounds, such as methyltrichlorosilane, tert-butyltrichlorosilane, silicon tetrachloride, and their bromides; general formula R4-nSnX n (Here, R represents a hydrocarbon group with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer from 3 to 4.) The tin halide compounds represented are, for example, methyltin trichloride, tert-butyltin trichloride, tin tetrachloride, and other polyhalides. Additionally, dimethyl carbonate, diethyl carbonate, etc., can also be used.

[0222] The conjugated diene copolymer (D) and the low molecular weight conjugated diene copolymer (E) of this embodiment are hydrogenated as needed. The hydrogenation reaction can be carried out using a known hydrogenation catalyst and a known method.

[0223] The solutions of the conjugated diene copolymer (D) and the low molecular weight conjugated diene copolymer (E) obtained in this embodiment as described above can be used to remove catalyst residues and separate the conjugated diene copolymer from the solution as needed.

[0224] When manufacturing conjugated diene copolymers using anionic living polymerization, compounds containing metal atoms in the polymerization initiator and the hydrogenation catalyst used in the aforementioned hydrogenation reaction react with moisture in the air during solvent removal processes, generating specific metal compounds that tend to remain in the conjugated diene copolymers. As described above, materials for electronic circuit boards preferably include a process in which each material is dissolved in an organic solvent and impurities such as the aforementioned metal compounds are removed by filtration. During filtration, metal compounds tend to clog filters such as screens, leading to reduced productivity.

[0225] Furthermore, if these metal compounds are included in the cured product of this embodiment, the dielectric constant and dielectric loss tangent tend to increase, thereby making them prone to ion migration in electronic material applications.

[0226] Examples of metal compounds that can remain in the conjugated diene copolymer of this embodiment include compounds containing metals in polymerization initiators and hydrogenation catalysts, such as oxides of each atom of titanium oxide, amorphous titanium oxide, orthotitanic acid, metatitanic acid, titanium hydroxide, nickel hydroxide, nickel monoxide, lithium oxide, lithium hydroxide, cobalt oxide, cobalt hydroxide, etc., and composite oxides of each atom of lithium titanate, barium titanate, strontium titanate, nickel titanate, nickel-iron oxide, etc., and dissimilar metals.

[0227] From the perspective of productivity, the residual amount of metal compounds in the conjugated diene copolymer (D) and the low molecular weight conjugated diene copolymer (E) of this embodiment is preferably 150 ppm or less, more preferably 130 ppm or less, further preferably 100 ppm or less, and even more preferably 90 ppm or less, in terms of residual metal content. In particular, from the perspective of particle size, Co is preferably 80 ppm or less, more preferably 60 ppm or less, further preferably 40 ppm or less, even more preferably 20 ppm or less, more preferably 10 ppm or less, even more preferably 5 ppm or less, and even more preferably 2 ppm or less.

[0228] Furthermore, from the perspectives of low dielectric constant, low dielectric loss tangent, and low ion migration, the residual metal content is preferably 80 ppm or less, more preferably 70 ppm or less, even more preferably 60 ppm or less, and even more preferably 50 ppm or less.

[0229] As a method for reducing the residual metal content in the conjugated diene copolymer (D) and the low molecular weight conjugated diene copolymer (E) of this embodiment, existing known methods can be applied, and there are no particular limitations. Examples include: adding water and carbon dioxide after the hydrogenation reaction of the conjugated diene copolymer to neutralize the hydrogenation catalyst residue; or adding an acid in addition to water and carbon dioxide to neutralize the hydrogenation catalyst residue. Specifically, the method described in Japanese Patent Application No. 2014-557427 can be used. Even with these methods for reducing residual metal content, since water containing metal compounds (hydroxides) is mixed in during the desolventizing process of the conjugated diene copolymer, the conjugated diene copolymer of this embodiment typically contains about 1 to 15 ppm. Therefore, relative to the amount of metal added to the conjugated diene copolymer, it is preferable to remove 20% or more, more preferably 30% or more, further preferably 40% or more, further more preferably 50% or more, and even more preferably 60% or more.

[0230] Furthermore, by reducing the amount of polymerization initiator and hydrogenation catalyst added, the residual metal content in the conjugated diene copolymer (D) and the low molecular weight conjugated diene copolymer (E) of this embodiment can also be reduced. However, if the amount of polymerization initiator is reduced, the molecular weight of the conjugated diene copolymer increases. If it is outside the preferred molecular weight range mentioned above, the strength of the cured product tends to decrease. In addition, if the amount of hydrogenation catalyst is reduced during the hydrogenation reaction, the hydrogenation reaction time will be longer and the hydrogenation reaction temperature will be higher, tending to significantly reduce productivity.

[0231] Examples of solvent separation methods for removing conjugated diene copolymers include: adding a polar solvent such as acetone or alcohol (which is a poor solvent for conjugated diene copolymers) to the hydrogenated reaction solution to precipitate the copolymers for recovery; immersing the reaction solution in hot water under stirring and removing the solvent by stripping; directly heating the conjugated diene copolymer solution and distilling to remove the solvent; and so on.

[0232] It should be noted that various phenolic stabilizers, phosphorus stabilizers, sulfur stabilizers, amine stabilizers, and other stabilizers can be added to the hydrides of conjugated diene copolymers.

[0233] The conjugated diene copolymer of this embodiment may have "polar groups" (excluding the free radical reactive groups of the vinyl aromatic monomer unit (a-1) with free radical reactive groups mentioned above) within a range that does not impair dielectric properties.

[0234] As a "polar group", examples include, but are not limited to, groups containing at least one functional group selected from the group consisting of hydroxyl, carboxyl, carbonyl, thiocarbonyl, acyl halide, acid anhydride, carboxylic acid, thiocarboxylic acid, aldehyde, thioaldehyde, carboxylic acid ester, amide, sulfonic acid, sulfonate, phosphoric acid, phosphate ester, amino, imino, nitrile, pyridinyl, quinolinyl, epoxy, thioepoxy, thioether, isocyanate, isothiocyanate, silyl halide, silanol, alkoxysilyl, tin halide, borate, boron-containing, borate, alkoxytin, and phenyltin.

[0235] The aforementioned "polar groups" can be formed using modifiers.

[0236] Examples of modifiers include, but are not limited to, tetraglycidyl-m-phenylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-epoxypropoxyethyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropyldimethylphenoxysilane, bis(γ-epoxypropoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolinone, 1,3-diethyl-2-imidazolinone, N,N'-dimethylacrylurea, N-methylpyrrolidone, maleic acid, maleic anhydride, maleic anhydride imide, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, glycidyl methacrylate, crotonic acid, etc.

[0237] As a method for forming "polar groups", any known method can be used, and there are no particular limitations.

[0238] Examples include melt mixing and methods that dissolve or disperse the components in a solvent to allow them to react. Other examples include methods that use functionalized polymerization initiators and unsaturated monomers with functional groups to polymerize via anionic living polymerization; methods that modify the active ends by adding modifiers that form or contain functional groups; methods that react organolithium compounds or other organoalkali metal compounds with conjugated diene copolymers (metallization reactions); and methods that involve adding functionalized modifiers to block polymers containing organoalkali metals.

[0239] [Resin Composition]

[0240] The resin composition of this embodiment includes the conjugated diene copolymer of this embodiment, or the conjugated diene copolymer composition of this embodiment (a conjugated diene copolymer composition including the above-mentioned conjugated diene copolymer (D) and the above-mentioned conjugated diene copolymer (E)) (component (I)), and at least one component selected from the group consisting of components (II) to (III) below.

[0241] Component (II): Free radical initiator

[0242] Component (III): Curing resin (excluding component (I))

[0243] It should be noted that the resin composition of this embodiment may contain the following components (IV), (V), and (VI).

[0244] Component (IV): Flame retardant

[0245] Composition (V): Filler

[0246] Component (VI): Crosslinking aid

[0247] (Component (II): Free radical initiator)

[0248] As a free radical initiator, existing known initiators can be used.

[0249] For example, thermal free radical initiators can be used as free radical initiators. Examples of such thermal free radical initiators include, but are not limited to, hydrogen peroxides such as dicumyl peroxide (Percumyl P), cumene hydroperoxide (Percumyl H), and tert-butyl peroxide (Perbutyl H); dialkyl peroxides such as α,α-bis(tert-butylperoxym-isopropyl)benzene (Perbutyl P); dicumyl peroxide (Percumyl D); 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (Perhexa 25B); tert-butyl cumyl peroxide (Perbutyl C); di-tert-butyl peroxide (Perbutyl D); 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne (Perhexyne 25B); tert-butyl peroxide (2-ethylhexanoate) (Perbutyl O); peroxide ketones; and 4,4-di(tert-butylperoxy)valerate (PERHEXA). V) such as peroxide ketals, peroxide diacyl, peroxide dicarbonate, peroxide esters and other organic peroxides, 2,2-azobisisobutyl nitrile, 1,1'-(cyclohexane-1-1-carboxynitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylpentanonitrile) and other azo compounds.

[0250] These substances can be used alone or in combination with more than one.

[0251] (Component (III): Curing resin)

[0252] Component (III): Curable resin refers to a resin that forms a polymeric network structure through polymerization reactions such as heating. From the perspective of the aforementioned polymerization reaction, the curable resin has a plurality of reactive groups. While there are no particular limitations on the polymerization reaction, from the perspective of reducing the dielectric loss tangent and lowering the dielectric constant, curing based on free radical reactions and addition reactions, or curing based on free radical reactions, is preferred. That is, component (III): the curable resin is preferably a free radical curable resin. Compared to free radical reactions, curing based on condensation reactions tends to require highly polar reactive groups and tends to have lower effects on reducing the dielectric loss tangent and lowering the dielectric constant.

[0253] Reactive groups that undergo curing via free radical reactions are chemical groups that can generate free radicals and / or induce the formation of free radicals through the action of heat and / or light and / or free radical initiators. Examples of chemical groups that generate free radicals primarily through light and / or free radical initiators include benzophenone groups, benzoyl groups, groups containing anthraquinone skeletons, and thioxanthone groups.

[0254] Furthermore, examples of chemical groups that generate free radicals through heat and / or light and / or free radical initiators include groups containing disulfide bonds and groups containing peroxide bonds. Examples of chemical groups that generate free radicals primarily through heat and / or free radical initiators include benzyl carbon having at least one hydrogen substituent, mercapto, vinyl, groups containing an alkoxyamine skeleton, groups containing an azo bond, maleimide, allyl, and methacryloyl groups. From the perspective of free radical reactivity, vinyl, maleimide, allyl, and methacryloyl groups are preferred.

[0255] (Ratio of component (I) to component (III))

[0256] By appropriately adjusting the SP value, the above-mentioned component (I): conjugated diene copolymer or conjugated diene copolymer composition, compared with the above-mentioned component (III): curable resin, specifically a resin having vinyl, maleimide, allyl, and methacryloyl groups, tends to have a good dielectric constant and dielectric loss tangent when used alone. Therefore, from the perspective of lower dielectric constant and lower dielectric loss tangent of the resin composition of this embodiment, the mass ratio of component (I) and component (III) in the resin composition of this embodiment is preferably component (I) / component (III) = 40 / 60 to 90 / 10, more preferably 50 / 50 to 85 / 15, and even more preferably 55 / 45 to 80 / 20.

[0257] Furthermore, from the perspective of reducing the dielectric constant and / or reducing the dielectric loss tangent of the resin composition of this embodiment, it is preferable not to include component (II): free radical initiator. However, it is preferable to appropriately adjust the amount of addition based on the free radical reactivity of components (I) and (III), curing temperature, curing time, considering the reduction of dielectric constant and the reduction of dielectric loss tangent, as well as the heat resistance and adhesion to the metal foil, and the balance of CTE.

[0258] (Component (IV): Flame retardant)

[0259] The resin composition of this embodiment may further include a flame retardant as a component (IV).

[0260] In addition, the flame retardant contained in the additives of the conjugated diene copolymer or conjugated diene copolymer composition as component (I) has the same meaning as component (IV) of the above-mentioned resin composition.

[0261] Examples of flame retardants include, but are not limited to, halogenated flame retardants such as bromine compounds, phosphorus-based flame retardants such as aromatic compounds, metal hydroxides, alkyl sulfonates, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, and aromatic bromine compounds including hexabromobenzene, decabromodiphenyl ethane, 4,4-dibromobiphenyl, and ethylenebistetrabromophthalimide.

[0262] These flame retardants can be used alone or in combination of two or more.

[0263] Among the aforementioned flame retardants are also so-called flame retardant additives, which exhibit low flame retardant performance on their own but achieve a better effect when used in combination with other flame retardants.

[0264] (Composition (V): Filler)

[0265] The resin composition of this embodiment may further include filler as a component (V).

[0266] In addition, the fillers included as additives in the conjugated diene copolymer or conjugated diene copolymer composition as component (I) have the same meaning as component (V) of the above-mentioned resin composition.

[0267] Examples of fillers include, but are not limited to, inorganic fillers such as silicon dioxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, barium sulfate, carbon black, glass fiber, glass beads, hollow glass spheres, glass flakes, graphite, titanium dioxide, potassium titanate whiskers, carbon fiber, alumina, kaolin, silica, calcium silicate, quartz, mica, talc, clay, zirconium oxide, potassium titanate, alumina, and metal particles; and organic fillers such as wood chips, wood powder, pulp, and cellulose nanofibers.

[0268] These substances can be used individually or in combination.

[0269] The shape of these fillers can be any shape, such as flakes, spheres, granules, powders, or amorphous shapes, without any particular limitation.

[0270] CTE tends to be optimized by including fillers. As fillers, silica is preferred. Examples of silica include amorphous silica, molten silica, crystalline silica, synthetic silica, hollow silica, etc.

[0271] Fillers and flame retardants can also be of the type that have been pre-treated with surface treatment agents such as silane coupling agents.

[0272] Examples of surface treatment agents include fluorinated silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. These substances can be used alone or in combination of two or more.

[0273] (Component (VI) Crosslinking Aid)

[0274] As a crosslinking aid, a low molecular weight compound having a structure with at least two reactive groups can be used.

[0275] Low molecular weight compounds having a structure with at least two reactive groups also have the function of reacting with component (I) and / or component (III) to cure the resin composition.

[0276] Examples of compounds having a structure with at least two reactive groups include, but are not limited to, allyl monomers such as triallyl isocyanurate (manufactured by Mitsubishi Chemical Co., Ltd., Taic), 1,2-bis(4-vinylphenyl)ethane, tris(2-hydroxyethyl) isocyanurate, diallyl fumarate, diallyl adipate, triallyl citrate, and diallyl hexahydrophthalate.

[0277] (Other additives)

[0278] The resin composition and / or cured product of this embodiment may contain other additives.

[0279] There are no particular restrictions on other additives, as long as they are commonly used in the mixing of resin compositions and / or cured products.

[0280] Other additives include, but are not limited to, pigments and / or colorants such as carbon black and titanium dioxide; lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bis-stearamide; anti-sticking agents; plasticizers such as organopolysiloxanes, phthalates, adipates, azelaic acid esters, and mineral oils; antioxidants such as hindered phenolic and phosphorus-based heat stabilizers; hindered amine light stabilizers; benzotriazole UV absorbers; antistatic agents; organic fillers; thickeners; defoamers; leveling agents; and resin additives such as adhesion promoters; other additives or mixtures thereof.

[0281] From the perspective of low dielectric constant and low dielectric loss tangent mentioned above, the resin composition of this embodiment is preferably free of pigments, colorants, lubricants, anti-sticking agents, and antistatic agents.

[0282] The resin composition in this embodiment may be formed by melting and mixing the components, or it may be formed by dissolving the components in a solvent and stirring (hereinafter referred to as "varnish"). From the perspective of processability, varnish is preferred.

[0283] Solvents used to constitute varnishes include, but are not limited to, ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, and γ-butyrolactone; acetates such as ethyl acetate, butyl acetate, acetic acid cellosolve, propylene glycol monomethyl ether acetate, carbitol acetate, and diethylene glycol monoethyl ether acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. A single solvent may be used, or two or more may be used in combination.

[0284] (Method for manufacturing the resin composition)

[0285] The method for manufacturing the resin composition of this embodiment is not particularly limited, and known methods can be used.

[0286] For example, methods such as using common mixers like Banbury mixers, single-screw extruders, twin-screw extruders, worm gear kneaders, and multi-screw extruders to melt and mix the components; methods of dissolving or dispersing the components and then heating to remove the solvent; etc. From the perspective of processability in producing molded articles suitable for electronic circuit board materials such as prepregs and resin films described later, the method of dissolving or dispersing the components and then heating to remove the solvent is preferred.

[0287] [cured material]

[0288] The cured product of this embodiment includes the conjugated diene copolymer described in this embodiment.

[0289] The cured product of this embodiment is the cured product of the conjugated diene copolymer, the conjugated diene copolymer composition, or the resin composition of this embodiment.

[0290] The cured product of this embodiment is obtained by subjecting the conjugated diene copolymer, conjugated diene copolymer composition, or resin composition of this embodiment to a curing reaction at any temperature and time. It includes, in addition to fully cured products, a partially cured product containing uncured components (semi-cured).

[0291] In the manufacturing process of the laminates described later, a process for further curing the cured material can be performed.

[0292] The reaction temperature of the curing process of the cured product in this embodiment is preferably 80°C or higher, more preferably 100°C or higher, and even more preferably 120°C or higher. The reaction time is preferably 10 to 240 minutes, more preferably 20 to 230 minutes, and even more preferably 30 to 220 minutes. When the resin composition of this embodiment is a varnish, the curing reaction is preferably carried out after the solvent is removed. As a drying method, it can be carried out by existing known methods such as heating or blowing hot air, and is preferably carried out at a low temperature below the curing reaction temperature. Regarding the amount of solvent in the cured product, drying is preferably carried out at 10% by mass or less, more preferably 5% by mass or less.

[0293] [Resin film]

[0294] The resin film of this embodiment comprises the resin composition of this embodiment.

[0295] The resin film of this embodiment is obtained, for example, by spreading a varnish composed of the resin composition of this embodiment on a suitable support to form a uniform thin film, drying it, and removing the solvent. This resin film can be wound into rolls for storage.

[0296] The resin film in this embodiment can be composed of a layered protective film, in which case it can be used by peeling off the protective film.

[0297] Examples of supporting materials include films made of plastic materials, metal foils, and release paper.

[0298] Regarding films made of plastic materials that serve as supports, examples include polyesters such as polyethylene terephthalate and polyethylene naphthalate, acrylics such as polycarbonate and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polysulfide (PES), polyetherketone, and polyimide. From the perspectives of availability and cost, polyethylene terephthalate and polyethylene naphthalate are preferred.

[0299] Examples of metal foils include copper foil and aluminum foil, with copper foil being preferred. Copper foil can be used as the metal foil, either as a single metal composed of copper or as an alloy of copper with other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0300] In addition, the surface of the support that is bonded to the resin composition layer can be treated with matte finish, corona treatment, antistatic treatment, and anti-sticking treatment.

[0301] [Prepreg]

[0302] The prepreg of this embodiment comprises a substrate and a resin composition of this embodiment impregnated or coated onto the substrate. That is, the prepreg of this embodiment is a composite of the resin composition of this embodiment and the substrate.

[0303] Prepregs are obtained, for example, by impregnating a substrate such as glass cloth into a varnish that is the resin composition of the present embodiment described above, and then removing the solvent by the drying method described above.

[0304] Examples of suitable substrates include various glass cloths such as roving, cloth, chopped strand mat, and surface mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloths; woven or nonwoven fabrics made from liquid crystal fibers such as fully aromatic polyamide fibers, fully aromatic polyester fibers, and polybenzoxazole fibers; natural fiber cloths such as cotton cloth, linen cloth, and felt; natural cellulose-based substrates such as carbon fiber cloth, kraft paper, cotton paper, and cloths made from paper-glass blended fibers; and polytetrafluoroethylene porous membranes. From the perspective of dielectric properties, glass cloth is preferred.

[0305] These substrates can be used alone or in combination of two or more.

[0306] The proportion of solid components in the prepreg, which are composed of the resin composition of this embodiment, is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. When the proportion of solid components composed of the resin composition is 30% by mass or more, the prepreg tends to have superior insulation reliability when used in applications such as electronic substrates. When the above proportion is 80% by mass or less, it tends to have superior mechanical properties such as rigidity when used in applications such as electronic substrates.

[0307] [laminated body]

[0308] The laminate of this embodiment has the resin film and metal foil described above.

[0309] Alternatively, the laminate in this embodiment may also be composed of a cured product having the above-described prepreg and a metal foil.

[0310] The laminate of this embodiment can be manufactured, for example, through the following steps: a step (a) of laminating a resin film composed of the resin composition of this embodiment onto a specified substrate to form a resin layer and obtaining a prepreg; a step (b) of heating and pressurizing the resin layer to planarize it and obtaining a cured prepreg; and a step (c) of further forming a specified wiring layer composed of metal foil on the resin layer; and so on.

[0311] In the above process (a), there is no particular limitation on the method of laminating the resin film on the substrate. For example, methods such as using a multi-stage press, a vacuum press, an atmospheric pressure laminator, or a laminator that heats and pressurizes under vacuum can be used for lamination. It is preferable to use a laminator that heats and pressurizes under vacuum.

[0312] In this method using a laminator, when an electronic circuit board is obtained using the laminate of this embodiment, even if the electronic circuit board has fine wiring circuits on its surface, the spaces between the circuits can be filled with resin without any pores. Furthermore, lamination can be performed in batches or continuously using rollers or the like.

[0313] Examples of substrates include, but are not limited to, glass epoxy boards, metal substrates, polyester substrates, polyimide substrates, polyphenylene ether substrates, and fluoropolymer substrates. The surfaces of the laminated resin layers on these substrates can be pre-roughened, and the number of substrate layers is not limited.

[0314] In step (b) above, the resin film laminated in step (a) and the substrate are heated and pressurized to flatten them. The conditions of step (b) above can be adjusted arbitrarily according to the type of substrate and the composition of the resin film, for example, preferably in the range of temperature 100 to 300°C, pressure 0.2 to 20 MPa, and time 30 to 180 minutes.

[0315] In step (c) above, the resin film and the substrate are heated and pressurized to further form a predetermined wiring layer composed of metal foil on the prepared resin layer. There is no particular limitation on the method for forming the wiring layer, and existing well-known methods can be cited, such as subtractive etching methods, semi-additive methods, etc.

[0316] The subtractive method is as follows: a resist layer with a shape corresponding to the desired pattern shape is formed on a metal layer, and the portion of the metal layer where the resist has been removed is dissolved and removed by a reagent through a subsequent development process, thereby forming the desired wiring.

[0317] The semi-addition method is as follows: a metal coating is formed on the surface of the resin layer using an electroless plating method, a plating resist layer with a shape corresponding to the desired pattern is formed on the metal coating, a metal layer is then formed by an electrolytic plating method, and the unwanted electroless plating layer is removed using reagents, etc., to form the desired wiring layer.

[0318] Furthermore, through holes and other pores can be formed in the resin layer as needed. There are no particular limitations on the method for forming these pores; existing known methods can be used. Examples of methods for forming pores include NC drill bits, carbon dioxide lasers, UV lasers, YAG lasers, and plasma.

[0319] Metal-coated laminate

[0320] The laminate described in this embodiment can be plate-shaped or flexible laminate.

[0321] The laminate in this embodiment can be a metal-clad laminate.

[0322] The metal-coated laminate is obtained by laminating the resin composition of this embodiment or the prepreg of this embodiment with a metal foil and then curing it, wherein a portion of the metal foil is removed.

[0323] Metal-clad laminates preferably have a form in which a cured prepreg (also known as a "cured composite") is laminated and bonded with a metal foil, and can be suitably used as a material for electronic circuit boards.

[0324] Examples of metal foils include aluminum foil and copper foil, with copper foil being preferred due to its low electrical resistance.

[0325] The cured prepreg combined with metal foil can be a single sheet or multiple sheets. Depending on the application, metal foil is stacked on one or both sides of the cured material and processed into a laminate.

[0326] As a method for manufacturing the above-mentioned metal-clad laminate, for example, the following method can be used: forming a prepreg composed of the resin composition of this embodiment and a substrate, stacking it with a metal foil, and then curing the resin composition, thereby obtaining a metal-clad laminate formed by laminating the cured prepreg with the metal foil.

[0327] One particularly preferred application of the aforementioned metal-clad laminate is in printed circuit boards. In printed circuit boards, it is preferable to remove at least a portion of the metal foil from the metal-clad laminate.

[0328] The aforementioned printed circuit board can be manufactured by pressurizing and heating the prepreg described in this embodiment. The same substrate as described above for the prepreg can be used as the substrate. The aforementioned printed circuit board, containing the resin composition of this embodiment, exhibits excellent strength and electrical properties (low dielectric constant and low dielectric loss tangent), thereby suppressing changes in electrical properties associated with environmental variations, and possesses excellent insulation reliability and mechanical properties.

[0329] Materials used for electronic circuit boards

[0330] The material used for the electronic circuit board in this embodiment includes a cured product of the resin composition of this embodiment.

[0331] The electronic circuit board used in this embodiment can be made using the resin composition and / or varnish described in this embodiment.

[0332] The material for the electronic circuit board of this embodiment includes at least one selected from the group consisting of a cured product of the above-described resin composition, a resin film containing the resin composition of this embodiment or a cured product thereof, and a prepreg that is a composite of a substrate and a resin composition. The material for the electronic circuit board of this embodiment can be used as a printed circuit board having a resin-coated metal foil.

[0333] Example

[0334] The following specific embodiments and comparative examples illustrate this implementation method in detail, but the present invention is not limited to the following embodiments and comparative examples.

[0335] The methods for structural identification and property determination of the conjugated diene copolymers or conjugated diene copolymer compositions (component (I)) used in the following examples and comparative examples are as follows.

[0336] [Methods for Structural Identification and Property Determination of Conjugated Diene Copolymers]

[0337] ((1) Content of vinyl aromatic monomer units in conjugated diene copolymers)

[0338] Using the unhydrogenated conjugated diene copolymer, the content of vinyl aromatic monomer units (a-1) and vinyl aromatic monomer units (a-2) (excluding the above unit (a-1)) with free radical reactive groups in the conjugated diene copolymer was determined using a nuclear magnetic resonance device (manufactured by BRUKER, DPX-400).

[0339] ((2) Vinyl bond content of conjugated diene copolymers)

[0340] The amount of vinyl bonding was determined using a pre-hydrogenated conjugated diene copolymer and an infrared spectrophotometer (FT / IR-230, manufactured by Nippon Spectrophotometer Co., Ltd.) to measure the amount of vinyl bonding.

[0341] The amount of vinyl bonds in conjugated diene copolymers was calculated using the Hampton method.

[0342] This value is taken as the content of 1,2-bonded and / or 3,4-bonded units when the total content of polymer blocks (B) and random polymer blocks (C) of the conjugated diene copolymer of component (I) is set to 100%.

[0343] (3) Number-average molecular weight of conjugated diene copolymers)

[0344] The number-average molecular weight of the (I) conjugated diene copolymer before modification and hydrogenation was determined using GPC [Apparatus: LC-10 (manufactured by Shimadzu Corporation), column: TSK gel GMHXL (4.6 mm × 30 cm)].

[0345] Tetrahydrofuran was used as the solvent. The determination was performed at 35°C. The number-average molecular weight was calculated as follows: a calibration curve was obtained based on the determination of commercially available standard polystyrene (using the peak molecular weight of the standard polystyrene), and the peak molecular weight of the chromatogram was determined using this calibration curve to obtain the number-average molecular weight.

[0346] It should be noted that the number-average molecular weight in the case of multiple peaks in a chromatogram is the average molecular weight calculated based on the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram).

[0347] ((4) Hydrogenation rate of double bonds in conjugated diene monomer units of conjugated diene copolymers)

[0348] The hydrogenation rate of the double bonds in the conjugated diene copolymers was determined using a nuclear magnetic resonance (NMR) instrument (BRUKER DPX-400).

[0349] (Ratio of free radical polymer block (C) in conjugated diene copolymers, ratio of unit (a-1) in polymer block (C), ratio of unit (a-2) in polymer block (C), ratio of unit (b) in polymer block (C))

[0350] Each time a vinyl aromatic compound (styrene and / or p-methylstyrene) and / or a conjugated diene compound (butadiene) constituting a block of a conjugated diene copolymer is added to the reactor, a sample of the polymerization solution before addition is taken. Approximately 20 mL of the sampled polymer solution is injected into a 100 mL bottle containing 0.50 mL of n-propylbenzene and approximately 20 mL of toluene, which is sealed as an internal standard, to prepare a sample for analysis.

[0351] The sample was measured using a gas chromatograph (Shimadzu Corporation: GC-14B) with a packed column loaded with Apison grease. The amount of residual monomer in the polymer solution was determined by the calibration curves of butadiene monomer, styrene monomer and p-methylstyrene obtained in advance, and the polymerization rate of butadiene monomer and / or styrene monomer and / or p-methylstyrene was confirmed to be 100%.

[0352] Therefore, the composition ratios of the free radical polymer block (C), the unit (a-1) ratio, the unit (a-2) ratio, and the unit (b) ratio in the conjugated diene copolymer are the same as the mass ratios of the added vinyl aromatic compound and the conjugated diene compound.

[0353] It should be noted that the polymerization rate of butadiene was determined at a constant temperature of 90℃, while the polymerization rate of styrene was determined under conditions of heating from 90℃ (held for 10 minutes) to 150℃ (10℃ / minute).

[0354] [Materials for conjugated diene copolymers, conjugated diene copolymer compositions, and resin compositions]

[0355] (Preparation of hydrogenation catalyst)

[0356] In the examples and comparative examples described later, the hydrogenation catalyst used in the production of conjugated diene copolymers was prepared by the following method.

[0357] The reaction vessel equipped with a stirring device was purged with nitrogen beforehand, and 1 liter of dried and purified cyclohexane was added into it.

[0358] Next, 100 mmol of bis(η5-cyclopentadiene)titanium dichloride was added. While stirring thoroughly, a hexane solution containing 200 mmol of trimethylaluminum was added, and the reaction was carried out at room temperature for about 3 days. This yielded the hydrogenation catalyst.

[0359] (Component (I): Conjugated diene copolymers and compositions of conjugated diene copolymers)

[0360] The following components (I) constituting the resin composition are prepared: conjugated diene copolymers, and each conjugated diene copolymer constituting a conjugated diene copolymer composition composed of two conjugated diene copolymers.

[0361] The structures and physical properties of the various conjugated diene copolymers are shown in Tables 1 to 4.

[0362] The constituent components and amounts of each component in each conjugated diene copolymer composition are shown in Tables 5 to 7.

[0363] It should be noted that in the table, (A) represents a polymer block (A) mainly composed of vinyl aromatic monomer units.

[0364] (B) represents a polymer block (B) with conjugated diene monomer units as the main component.

[0365] (C) represents a random polymer block (C) composed of vinyl aromatic monomer units and conjugated diene monomer units.

[0366] <Example 1: Conjugated diene copolymer (D1)>

[0367] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0368] First, add a cyclohexane solution (concentration 20% by mass) containing 7.5 parts by mass of styrene and 7.5 parts by mass of p-methylstyrene.

[0369] Next, 0.19 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0370] Next, a cyclohexane solution containing 60 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 45 minutes.

[0371] Next, a cyclohexane solution (concentration 20% by mass) containing 7.5 parts by mass of styrene and 7.5 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 15 minutes.

[0372] Next, a cyclohexane solution containing 2.5 parts by mass of styrene, 2.5 parts by mass of p-methylstyrene, and 5 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 10 minutes.

[0373] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0374] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 17.5%, unit (a-2) has a mass percentage of 17.5%, and the number-average molecular weight is 5.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 49%.

[0375] Add the hydrogenation catalyst prepared above to the obtained conjugated diene copolymer at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti), and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D1).

[0376] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene copolymer (D1). The hydrogenation rate was 97%.

[0377] <Example 2: Conjugated diene copolymer (D2)>

[0378] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0379] First, add a cyclohexane solution (concentration 20% by mass) containing 3.7 parts by mass of styrene and 11.3 parts by mass of p-methylstyrene.

[0380] Next, 0.19 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0381] Next, a cyclohexane solution containing 60 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 45 minutes.

[0382] Next, a cyclohexane solution (concentration 20% by mass) containing 3.7 parts by mass of styrene and 11.3 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 15 minutes.

[0383] Next, a cyclohexane solution containing 1.25 parts by mass of styrene, 3.75 parts by mass of p-methylstyrene, and 5 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 10 minutes.

[0384] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0385] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 26.3%, unit (a-2) has a mass percentage of 8.75%, and the number-average molecular weight is 5.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 51%.

[0386] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti) to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 0.75 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D2).

[0387] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were added as a stabilizer relative to 100 parts by weight of the conjugated diene copolymer (D2). The hydrogenation rate was 45%.

[0388] <Example 3: Conjugated diene copolymer (D3)>

[0389] The hydrogenation reaction time is 1 hour, otherwise the same operation as the conjugated diene copolymer (D2) is performed.

[0390] In the conjugated diene copolymer (D3) obtained above, unit (a-1) has a mass percentage of 26.3%, unit (a-2) has a mass percentage of 8.75%, and the number-average molecular weight is 5.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 55%.

[0391] <Example 4: Conjugated diene copolymer (D4)>

[0392] The hydrogenation reaction time was 1.5 hours, and otherwise the same operation as for the conjugated diene copolymer (D2) was performed.

[0393] In the conjugated diene copolymer (D4) obtained above, unit (a-1) has a mass percentage of 26.3%, unit (a-2) has a mass percentage of 8.75%, and the number-average molecular weight is 5.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 97%.

[0394] <Example 5: Conjugated diene copolymer (D5)>

[0395] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0396] First, add a cyclohexane solution (concentration 20% by mass) containing 0.7 parts by mass of styrene and 14.3 parts by mass of p-methylstyrene.

[0397] Next, 0.19 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0398] Next, a cyclohexane solution containing 60 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 45 minutes.

[0399] Next, a cyclohexane solution (concentration 20% by mass) containing 0.7 parts by mass of styrene and 14.3 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 15 minutes.

[0400] Next, a cyclohexane solution containing 0.25 parts by mass of styrene, 4.75 parts by mass of p-methylstyrene, and 5 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 10 minutes.

[0401] Methanol was then added to stop the polymerization reaction. Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (D5) to obtain the conjugated diene copolymer (D5).

[0402] In the conjugated diene copolymer (D5) obtained above, unit (a-1) has a mass percentage of 33.3%, unit (a-2) has a mass percentage of 1.7%, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 51%.

[0403] <Example 6: Conjugated diene copolymer (D6)>

[0404] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm (based on Ti) per 100 parts by mass of the conjugated diene copolymer (D5) obtained by the same operation as in Example 5, and carry out a hydrogenation reaction for about 0.75 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C to obtain the conjugated diene copolymer (D6).

[0405] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were added as a stabilizer relative to 100 parts by weight of the conjugated diene copolymer (D6).

[0406] In the conjugated diene copolymer (D6) obtained above, unit (a-1) has a mass percentage of 33.3%, unit (a-2) has a mass percentage of 8.75%, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.7, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 45%.

[0407] <Example 7: Conjugated diene copolymer (D7)>

[0408] The hydrogenation reaction time is 1 hour, otherwise the same operation as the conjugated diene copolymer (D6) is performed.

[0409] In the conjugated diene copolymer (D7) obtained above, unit (a-1) accounts for 33.3% by mass, unit (a-2) accounts for 1.7% by mass, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 51%, and the hydrogenation rate is 55%.

[0410] <Example 8: Conjugated diene copolymer (D8)>

[0411] The hydrogenation reaction time was 1.5 hours, and otherwise the same operation as for the conjugated diene copolymer (D6) was performed.

[0412] In the conjugated diene copolymer (D8) obtained above, unit (a-1) accounts for 33.3% by mass, unit (a-2) accounts for 1.7% by mass, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 51%, and the hydrogenation rate is 97%.

[0413] <Example 9: Conjugated diene copolymer (D9)>

[0414] The hydrogenation reaction time was set to 1.75 hours, and otherwise the same procedures were performed as for the conjugated diene copolymer (D6).

[0415] In the conjugated diene copolymer (D9) obtained above, unit (a-1) has a mass percentage of 33.3%, unit (a-2) has a mass percentage of 1.7%, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 99.5%.

[0416] <Example 10: Conjugated diene copolymer (D10)>

[0417] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0418] First, add a cyclohexane solution (concentration 20% by mass) containing 1.2 parts by mass of styrene and 23.8 parts by mass of p-methylstyrene.

[0419] Next, 0.16 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 20 minutes.

[0420] Next, a cyclohexane solution containing 45 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 45 minutes.

[0421] Next, a cyclohexane solution (concentration 20% by mass) containing 1.2 parts by mass of styrene and 23.8 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 15 minutes.

[0422] Next, a cyclohexane solution containing 0.25 parts by mass of styrene, 4.75 parts by mass of p-methylstyrene, and 5 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 10 minutes.

[0423] Then methanol was added to stop the polymerization reaction.

[0424] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 52.3%, unit (a-2) has a mass percentage of 7.7%, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 49%.

[0425] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti) to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D10).

[0426] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (D10). The hydrogenation rate was 97%.

[0427] <Example 11: Conjugated diene copolymer (D11)>

[0428] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0429] First, add a cyclohexane solution (concentration 20% by mass) containing 1.9 parts by mass of styrene and 5.6 parts by mass of p-methylstyrene.

[0430] Next, 0.16 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.6 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 7 minutes.

[0431] Next, a cyclohexane solution containing 55 parts by mass of butadiene, 1 part by mass of styrene, and 19 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 45 minutes.

[0432] Next, a cyclohexane solution (concentration 20% by mass) containing 1.9 parts by mass of styrene and 5.6 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 7 minutes.

[0433] Next, a cyclohexane solution containing 10 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 10 minutes.

[0434] Then methanol was added to stop the polymerization reaction.

[0435] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 33.3%, unit (a-2) has a mass percentage of 1.7%, and the number-average molecular weight is 5.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0436] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti) to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D11).

[0437] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (D11). The hydrogenation rate was 97%.

[0438] <Example 12: Conjugated diene copolymer (D12)>

[0439] The n-butyllithium was made to be 0.093 parts by mass relative to 100 parts by mass of all monomers, and otherwise the same operation as that for the conjugated diene copolymer (D11) was performed.

[0440] In the conjugated diene copolymer (D12) obtained above, unit (a-1) has a mass percentage of 33.3%, unit (a-2) has a mass percentage of 1.7%, and the number-average molecular weight is 10.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 49%, and the hydrogenation rate is 97%.

[0441] <Example 13: Conjugated diene copolymer (D13)>

[0442] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0443] First, add a cyclohexane solution (concentration 20% by mass) containing 0.5 parts by mass of styrene and 9.5 parts by mass of p-methylstyrene.

[0444] Next, 0.16 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.6 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 10 minutes.

[0445] Next, a cyclohexane solution containing 25 parts by mass of butadiene, 1.7 parts by mass of styrene, and 33.3 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 45 minutes.

[0446] Next, a cyclohexane solution (concentration 20% by mass) containing 0.5 parts by mass of styrene and 9.5 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 10 minutes.

[0447] Next, a cyclohexane solution containing 20 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 15 minutes.

[0448] Then methanol was added to stop the polymerization reaction.

[0449] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 52.3%, unit (a-2) has a mass percentage of 2.7%, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 49%.

[0450] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti) to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D13).

[0451] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were added as a stabilizer relative to 100 parts by weight of the conjugated diene copolymer (D13). The hydrogenation rate was 97%.

[0452] <Example 14: Conjugated diene copolymer (D14)>

[0453] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0454] First, add a cyclohexane solution (concentration 20% by mass) containing 0.5 parts by mass of styrene and 9.5 parts by mass of p-methylstyrene.

[0455] Next, 0.16 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.6 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 10 minutes.

[0456] Next, a cyclohexane solution containing 10 parts by mass of butadiene, 1.7 parts by mass of styrene, and 33.3 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 35 minutes.

[0457] Next, a cyclohexane solution (concentration 20% by mass) containing 0.5 parts by mass of styrene and 9.5 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 10 minutes.

[0458] Next, a cyclohexane solution containing 35 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 20 minutes.

[0459] Then methanol was added to stop the polymerization reaction.

[0460] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 52.3%, unit (a-2) has a mass percentage of 2.7%, and the number-average molecular weight is 5.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 49%.

[0461] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti) to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D14).

[0462] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were added as a stabilizer relative to 100 parts by weight of the conjugated diene copolymer (D14). The hydrogenation rate was 97%.

[0463] <Example 15: Conjugated diene copolymer (D15)>

[0464] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0465] First, add a cyclohexane solution (concentration 20% by mass) containing 11.3 parts by mass of styrene and 3.8 parts by mass of p-methylstyrene.

[0466] Next, 0.19 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0467] Next, a cyclohexane solution containing 60 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 45 minutes.

[0468] Next, a cyclohexane solution (concentration 20% by mass) containing 11.3 parts by mass of styrene and 3.8 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 15 minutes.

[0469] Next, a cyclohexane solution containing 3.7 parts by mass of styrene, 1.3 parts by mass of p-methylstyrene, and 5 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 10 minutes.

[0470] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0471] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 8.75%, unit (a-2) has a mass percentage of 6.25%, and the number-average molecular weight is 5.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 49%.

[0472] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti) to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D15).

[0473] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were added as a stabilizer relative to 100 parts by weight of the conjugated diene copolymer (D15). The hydrogenation rate was 97%.

[0474] <Example 16: Conjugated diene copolymer (D22)>

[0475] The same operation as that for the conjugated diene copolymer (D8) was performed, except that the ratio of n-butyllithium to 0.0889 parts by mass relative to 100 parts by mass of all monomers was made.

[0476] In the conjugated diene copolymer (D22) obtained above, unit (a-1) has a mass percentage of 33.3%, unit (a-2) has a mass percentage of 1.7%, and the number-average molecular weight is 10.5 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 51%, and the hydrogenation rate is 97%.

[0477] <Example 63-1: Conjugated diene copolymer (D23) used in Example 63 described later>

[0478] As described below, in the conjugated diene copolymer composition (X22) of Examples 63-3, conjugated diene copolymer (D23) and conjugated diene copolymer (E13) were prepared using a reactor to obtain the conjugated diene copolymer composition (X22) formed therefrom.

[0479] The properties of the conjugated diene copolymer (D23) are shown in Table 2.

[0480] <Example 64-1: Conjugated diene copolymer (D24) used in Example 64 described later>

[0481] As described below, in the conjugated diene copolymer composition (X23) of Examples 64-3, conjugated diene copolymer (D24) and conjugated diene copolymer (E14) were prepared using a reactor to obtain the conjugated diene copolymer composition (X23) formed therefrom.

[0482] The properties of the conjugated diene copolymer (D24) are shown in Table 2.

[0483] <Example 65-1: Conjugated diene copolymer (D25) used in Example 65 described later>

[0484] As described below, in the conjugated diene copolymer composition (X24) of Examples 65-3, conjugated diene copolymer (D25) and conjugated diene copolymer (E15) were prepared using a reactor to obtain the conjugated diene copolymer composition (X24) formed therefrom.

[0485] The properties of the conjugated diene copolymer (D25) are shown in Table 2.

[0486] <Manufacturing Example 1: Conjugated Diene Copolymer (E1)>

[0487] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0488] First, add a cyclohexane solution (concentration 20% by mass) containing 11.5 parts by mass of styrene and 11.5 parts by mass of p-methylstyrene.

[0489] Next, 0.80 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0490] Next, a cyclohexane solution containing 38 parts by mass of butadiene, 19.5 parts by mass of styrene, and 19.5 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 50 minutes.

[0491] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0492] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 31%, unit (a-2) has a mass percentage of 31%, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0493] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti) to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (E1).

[0494] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (E1). The hydrogenation rate was 97%.

[0495] <Manufacturing Example 2: Conjugated Diene Copolymer (E2)>

[0496] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0497] First, add a cyclohexane solution (concentration 20% by mass) containing 5.8 parts by mass of styrene and 17.3 parts by mass of p-methylstyrene.

[0498] Next, 0.80 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0499] Next, a cyclohexane solution containing 38 parts by mass of butadiene, 9.8 parts by mass of styrene, and 29.3 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 50 minutes.

[0500] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0501] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 46.5%, unit (a-2) has a mass percentage of 15.5%, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0502] Add the hydrogenation catalyst prepared above to the obtained conjugated diene copolymer at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti), and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (E2).

[0503] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (E2). The hydrogenation rate was 97%.

[0504] <Manufacturing Example 3: Conjugated Diene Copolymer (E3)>

[0505] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0506] First, add a cyclohexane solution (concentration 20% by mass) containing 1.2 parts by mass of styrene and 21.9 parts by mass of p-methylstyrene.

[0507] Next, 0.80 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0508] Next, a cyclohexane solution containing 38 parts by mass of butadiene, 1.9 parts by mass of styrene, and 37.1 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 50 minutes.

[0509] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer. Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (E3). The hydrogenation rate was 97%.

[0510] In the conjugated diene copolymer obtained above, unit (a-1) accounts for 58.9% by mass, unit (a-2) accounts for 3.1% by mass, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0511] <Manufacturing Example 4: Conjugated Diene Copolymer (E4)>

[0512] The same procedure as for the conjugated diene copolymer (E3) was performed, adding 90 ppm of the hydrogenation catalyst prepared above relative to 100 parts by mass of the conjugated diene copolymer (based on Ti) to the obtained conjugated diene copolymer, and carrying out the hydrogenation reaction for about 0.75 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (E4).

[0513] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (E4).

[0514] In the conjugated diene copolymer obtained above, unit (a-1) accounts for 58.9% by mass, unit (a-2) accounts for 3.1% by mass, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 45%.

[0515] <Manufacturing Example 5: Conjugated Diene Copolymer (E5)>

[0516] The hydrogenation reaction time is 1 hour, otherwise the same operation as the conjugated diene copolymer (E4) is performed.

[0517] In the conjugated diene copolymer obtained above, unit (a-1) accounts for 58.9% by mass, unit (a-2) accounts for 3.1% by mass, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 55%.

[0518] <Manufacturing Example 6: Conjugated Diene Copolymer (E6)>

[0519] The hydrogenation reaction time was 1.5 hours, and otherwise the same operation as for the conjugated diene copolymer (E4) was performed.

[0520] In the conjugated diene copolymer obtained above, unit (a-1) accounts for 58.9% by mass, unit (a-2) accounts for 3.1% by mass, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 97%.

[0521] <Manufacturing Example 7: Conjugated Diene Copolymer (E7)>

[0522] The n-butyllithium was made to be 0.40 parts by mass relative to 100 parts by mass of all monomers, and the hydrogenation reaction time was 1.5 hours. Otherwise, the same operation as for the conjugated diene copolymer (E4) was carried out.

[0523] In the conjugated diene copolymer obtained above, unit (a-1) accounts for 58.9% by mass, unit (a-2) accounts for 3.1% by mass, and the number-average molecular weight is 2.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 97%.

[0524] <Manufacturing Example 8: Conjugated Diene Copolymer (E8)>

[0525] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0526] First, add a cyclohexane solution (concentration 20% by mass) containing 2.5 parts by mass of styrene, 47.5 parts by mass of p-methylstyrene, and 50 parts by mass of butadiene.

[0527] Next, 0.80 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 80 minutes.

[0528] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0529] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 47.5%, unit (a-2) has a mass percentage of 2.5%, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0530] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to Ti per 100 parts by mass of the conjugated diene copolymer to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (E8).

[0531] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (E8). The hydrogenation rate was 97%.

[0532] <Manufacturing Example 9: Conjugated Diene Copolymer (E9)>

[0533] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0534] First, add a cyclohexane solution (concentration 20% by mass) containing 1.6 parts by mass of styrene and 31.4 parts by mass of p-methylstyrene.

[0535] Next, 0.92 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.6 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 25 minutes.

[0536] Next, a cyclohexane solution containing 67 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 50 minutes.

[0537] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0538] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 31.4%, unit (a-2) has a mass percentage of 1.6%, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 70%.

[0539] Add the hydrogenation catalyst prepared above to the obtained conjugated diene copolymer at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti), and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (E9).

[0540] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (E9). The hydrogenation rate was 97%.

[0541] <Manufacturing Example 10: Conjugated Diene Copolymer (E10)>

[0542] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0543] First, add a cyclohexane solution (concentration 20% by mass) containing 1.0 part by mass of styrene and 19 parts by mass of p-methylstyrene.

[0544] Next, 1.07 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0545] Next, a cyclohexane solution containing 80 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 60 minutes.

[0546] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0547] In the conjugated diene copolymer obtained above, unit (a-1) accounts for 19% by mass, unit (a-2) accounts for 1.0% by mass, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0548] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to Ti per 100 parts by mass of the conjugated diene copolymer to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (E10).

[0549] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (E10). The hydrogenation rate was 97%.

[0550] <Manufacturing Example 11: Conjugated Diene Copolymer (E11)>

[0551] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0552] First, add a cyclohexane solution (concentration 20% by mass) containing 0.6 parts by mass of styrene and 11.9 parts by mass of p-methylstyrene.

[0553] Next, 1.07 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.3 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0554] Next, a cyclohexane solution containing 80 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 65 minutes.

[0555] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0556] In the conjugated diene copolymer obtained above, unit (a-1) accounts for 11.9% by mass, unit (a-2) accounts for 0.6% by mass, and the number-average molecular weight is 1.0 × 10⁻⁶. 4The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0557] The prepared hydrogenation catalyst was added to the obtained conjugated diene copolymer at a concentration of 90 ppm (based on Ti) relative to 100 parts by mass of block copolymer, and the hydrogenation reaction was carried out for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (E11).

[0558] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (E11). The hydrogenation rate was 97%.

[0559] <Comparative Manufacturing Example 12: Conjugated Diene Copolymer (E12)>

[0560] All styrene was converted to p-methylstyrene, and otherwise the same operation as with conjugated diene copolymers (E6) was performed.

[0561] In the conjugated diene copolymer (E12) obtained above, unit (a-1) has a mass percentage of 0%, unit (a-2) has a mass percentage of 100%, and the number-average molecular weight is 1.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 51%, and the hydrogenation rate is 97%.

[0562] It should be noted that, regarding "polymer block (C)", in the above item (component (I): conjugated diene copolymer and conjugated diene copolymer composition), it is defined as "a random polymer block (C) containing vinyl aromatic monomer units and conjugated diene monomer units." Therefore, it is also referred to as having polymer block (C) in (E12).

[0563] <Manufacturing Example 63-2: Conjugated diene copolymer (E13) used in Example 63 described later>

[0564] As described below, in the conjugated diene copolymer composition (X22) of Examples 63-3, conjugated diene copolymer (D23) and conjugated diene copolymer (E13) were prepared using a reactor to obtain the conjugated diene copolymer composition (X22) formed therefrom.

[0565] The hydrogenation rate of the conjugated diene copolymer (E13) is 97%.

[0566] <Manufacturing Example 64-2: Conjugated diene copolymer (E14) used in Example 64 described later>

[0567] As described below, in the conjugated diene copolymer composition (X23) of Examples 64-3, conjugated diene copolymer (D24) and conjugated diene copolymer (E14) were prepared using a reactor to obtain the conjugated diene copolymer (X23) formed therefrom.

[0568] The hydrogenation rate of the conjugated diene copolymer (E14) is 97%.

[0569] <Manufacturing Example 65-2: Conjugated diene copolymer (E15) used in Example 65 described later>

[0570] As described below, in the conjugated diene copolymer composition (X24) of Examples 65-3, conjugated diene copolymer (D25) and conjugated diene copolymer (E15) were prepared using a reactor to obtain the conjugated diene copolymer (X24) formed therefrom.

[0571] The hydrogenation rate of the conjugated diene copolymer (E15) is 97%.

[0572] Comparative Example 1: Conjugated diene copolymer (D16)

[0573] Replace all p-methylstyrene with styrene, and otherwise perform the same operation as with the conjugated diene copolymer (D8).

[0574] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 0.0%, unit (a-2) has a mass percentage of 35%, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 97%.

[0575] It should be noted that, regarding "polymer block (C)", in the above item (component (I): conjugated diene copolymer and conjugated diene copolymer composition), it is defined as "a random polymer block (C) containing vinyl aromatic monomer units and conjugated diene monomer units." Therefore, it is also recorded as having polymer block (C) in (D16).

[0576] Comparative Example 2: Conjugated diene copolymer (D17)

[0577] The n-butyllithium was made to be 0.0468 parts by mass relative to 100 parts by mass of all monomers, and otherwise the same operation as that for the conjugated diene copolymer (D8) was performed.

[0578] In the conjugated diene copolymer (D17) obtained above, unit (a-1) has a mass percentage of 33.3%, unit (a-2) has a mass percentage of 1.7%, and the number-average molecular weight is 20 × 10⁻⁶.4 The molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond content) is 50%, and the hydrogenation rate is 97%.

[0579] Comparative Example 3: Conjugated diene copolymer (D18)

[0580] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0581] First, add a cyclohexane solution (concentration 20% by mass) containing 2.0 parts by mass of styrene and 38 parts by mass of p-methylstyrene.

[0582] Next, 0.32 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.35 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 40 minutes.

[0583] Next, a cyclohexane solution containing 15 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 10 minutes.

[0584] Next, a cyclohexane solution (concentration 20% by mass) containing 2.0 parts by mass of styrene and 38 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 40 minutes.

[0585] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0586] In the conjugated diene copolymer obtained above, unit (a-1) accounts for 80.8% by mass, unit (a-2) accounts for 4.2% by mass, and the number-average molecular weight is 5.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0587] Add the hydrogenation catalyst prepared above at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti) to the obtained conjugated diene copolymer, and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D18).

[0588] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were added as a stabilizer relative to 100 parts by weight of the conjugated diene copolymer (D18). The hydrogenation rate was 97%.

[0589] Comparative Example 4: Conjugated diene copolymer (D19)

[0590] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0591] First, add a cyclohexane solution (concentration 20% by mass) containing 0.9 parts by mass of styrene and 16.6 parts by mass of p-methylstyrene.

[0592] Next, 0.32 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.19 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 15 minutes.

[0593] Next, a cyclohexane solution containing 65 parts by mass of butadiene was added, and polymerization was carried out at 60°C for 60 minutes.

[0594] Next, a cyclohexane solution (concentration 20% by mass) containing 0.9 parts by mass of styrene and 16.6 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 15 minutes.

[0595] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0596] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 33.3%, unit (a-2) has a mass percentage of 1.7%, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0597] Add the hydrogenation catalyst prepared above to the obtained conjugated diene copolymer at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti), and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D19).

[0598] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (D19). The hydrogenation rate was 97%.

[0599] Comparative Example 5: Conjugated diene copolymer (D20)

[0600] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0601] First, add a cyclohexane solution (concentration 20% by mass) containing 0.4 parts by mass of styrene and 7.1 parts by mass of p-methylstyrene.

[0602] Next, 0.32 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.19 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 60°C for 10 minutes.

[0603] Next, a cyclohexane solution containing 65 parts by mass of butadiene, 1 part by mass of styrene, and 19 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 65 minutes.

[0604] Next, a cyclohexane solution (concentration 20% by mass) containing 0.4 parts by mass of styrene and 7.1 parts by mass of p-methylstyrene was added, and polymerization was carried out at 60°C for 10 minutes.

[0605] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer.

[0606] In the conjugated diene copolymer obtained above, unit (a-1) has a mass percentage of 33.3%, unit (a-2) has a mass percentage of 1.7%, and the number-average molecular weight is 5.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, and the content of units derived from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0607] Add the hydrogenation catalyst prepared above to the obtained conjugated diene copolymer at a concentration of 90 ppm relative to 100 parts by mass of the conjugated diene copolymer (based on Ti), and carry out the hydrogenation reaction for about 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C to obtain the conjugated diene copolymer (D20).

[0608] Next, 0.25 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were added as a stabilizer relative to 100 parts by weight of the conjugated diene polymer (D20). The hydrogenation rate was 97%.

[0609] <Examples 17-32>, <Comparative Examples 6-10>

[0610] The conjugated diene copolymers ((D) component and (E) component) were mixed in the proportions shown in Tables 5 to 7 below to obtain the conjugated diene copolymer composition ((X) component).

[0611] <Example 63-3: Conjugated diene copolymer composition (X22)>

[0612] In the conjugated diene copolymer composition (X22), firstly, the conjugated diene copolymer (D23) and the conjugated diene copolymer (E13) are batch polymerized in a reactor, and then hydrogenation is carried out to obtain the conjugated diene copolymer composition (X22) composed of the conjugated diene copolymer (D23) and the conjugated diene copolymer (E13).

[0613] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0614] First, add a cyclohexane solution (concentration 20% by mass) containing 0.52 parts by mass of styrene and 9.98 parts by mass of p-methylstyrene.

[0615] Next, 0.125 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 10 minutes.

[0616] Next, a cyclohexane solution containing 42 parts by mass of butadiene (concentration 20 by mass) was added, and polymerization was carried out at 70°C for 25 minutes.

[0617] Next, 0.214 parts by mass of n-butyllithium (NBL2) relative to 100 parts by mass of all monomers and 0.4 mol of TMEDA relative to 1 mol of NBL2 were added. Then, a cyclohexane solution (concentration 25% by mass) containing 1.4 parts by mass of styrene and 27.1 parts by mass of p-methylstyrene was added, and polymerization was carried out at 70°C for 20 minutes.

[0618] Next, a cyclohexane solution (concentration 20% by mass) containing 9.5 parts by mass of butadiene, 0.02 parts by mass of styrene, and 9.03 parts by mass of p-methylstyrene was added, and polymerization was carried out at 70°C for 10 minutes.

[0619] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer composition (X22).

[0620] In the conjugated diene copolymer composition (X22) obtained above, the content of vinyl aromatic monomer units in the conjugated diene copolymer (D23) is 35% by mass, the amount of vinyl aromatic monomers in the random polymer block (C) of the conjugated diene copolymer (D23) is 5% by mass, the number average molecular weight is 51,000, the molecular weight distribution is 1.10, and the content of units from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 51%.

[0621] In the conjugated diene copolymer composition (X22) obtained above, the content of vinyl aromatic monomer units in the conjugated diene copolymer (E13) is 72% by mass, the content of vinyl aromatic monomers in the random polymer block (C) of the conjugated diene copolymer (E23) is 5% by mass, the number average molecular weight is 10,000, the molecular weight distribution is 1.10, and the content of units from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 50%.

[0622] The hydrogenation catalyst prepared above was added to the obtained conjugated diene copolymer composition (X22) at a concentration of 90 ppm relative to 100 parts by mass of block copolymer based on Ti. The hydrogenation reaction was carried out for about 1.5 hours under the conditions of hydrogen pressure 0.7 MPa and temperature 80 °C to obtain a solution of hydrogenated block copolymer.

[0623] The hydrogenation rate of the obtained conjugated diene copolymer composition (X22) was 97%.

[0624] The mass ratio of the obtained conjugated diene copolymer (D23) to the conjugated diene copolymer (E13) is (D23) / (E13) = 70 / 30.

[0625] <Example 64-3: Conjugated diene copolymer composition (X23)>

[0626] In the conjugated diene copolymer composition (X23), firstly, the conjugated diene copolymer (D24) and the conjugated diene copolymer (E14) are batch polymerized in a reactor, and then hydrogenation is carried out to obtain the conjugated diene copolymer composition (X23) containing the conjugated diene copolymer (D24) and the conjugated diene copolymer (E14).

[0627] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0628] First, add a cyclohexane solution (concentration 20% by mass) containing 0.3 parts by mass of styrene and 6.5 parts by mass of p-methylstyrene.

[0629] Next, 0.048 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.5 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 7 minutes.

[0630] Next, a cyclohexane solution (concentration 20% by mass) containing 2.3 parts by mass of butadiene, 2.2 parts by mass of styrene, and 0.1 parts by mass of p-methylstyrene was added, and polymerization was carried out at 70°C for 5 minutes.

[0631] Next, a cyclohexane solution containing 11.3 parts by mass of butadiene (concentration 20 by mass) was added, and polymerization was carried out at 70°C for 10 minutes.

[0632] Next, 0.117 parts by mass of n-butyllithium (NBL2) relative to 100 parts by mass of all monomers and 0.4 mol of TMEDA relative to 1 mol of NBL2 were added. Then, a cyclohexane solution containing 54.3 parts by mass of butadiene (concentration 25 by mass) was added, and polymerization was carried out at 70°C for 25 minutes.

[0633] Next, a cyclohexane solution (concentration 20% by mass) containing 1.2 parts by mass of styrene and 22.1 parts by mass of p-methylstyrene was added, and polymerization was carried out at 70°C for 15 minutes.

[0634] Methanol was then added to stop the polymerization reaction, yielding a conjugated diene copolymer composition (X23).

[0635] In the conjugated diene copolymer composition (X23) obtained above, the content of vinyl aromatic monomer units in the conjugated diene copolymer (D24) is 35% by mass, the amount of vinyl aromatic monomers in the random polymer block (C) of the conjugated diene copolymer (D24) is 5% by mass, the number average molecular weight is 88,000, the molecular weight distribution is 1.10, and the content of units from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 51%.

[0636] In the conjugated diene copolymer composition (X23) obtained above, the content of vinyl aromatic monomer units in the conjugated diene copolymer (E14) is 30% by mass, the number average molecular weight is 31,000, the molecular weight distribution is 1.10, and the content of units from 1,2-bonded and / or 3,4-bonded units (vinyl bond amount) is 50%.

[0637] The hydrogenation catalyst prepared above was added to the obtained conjugated diene copolymer composition (X23) at a concentration of 90 ppm relative to 100 parts by mass of block copolymer based on Ti. The hydrogenation reaction was carried out for about 1.5 hours under the conditions of hydrogen pressure 0.7 MPa and temperature 80 °C to obtain a solution of hydrogenated block copolymer.

[0638] The hydrogenation rate of the obtained conjugated diene copolymer composition (X23) was 97%.

[0639] The mass ratio of the obtained conjugated diene copolymer (D24) to the conjugated diene copolymer (E14) is (D24) / (E14) = 45 / 55.

[0640] <Example 65-3: Conjugated diene copolymer composition (X24)>

[0641] Make NBL2 to 0.88 parts by mass, and otherwise perform the same operation as for the conjugated diene copolymer composition (X23) to produce a conjugated diene copolymer (X24) comprising conjugated diene copolymer (D25) and conjugated diene copolymer (E15).

[0642] In the conjugated diene copolymer composition (X23) obtained above, the content of vinyl aromatic monomer units in the conjugated diene copolymer (D25) is 35% by mass, the amount of vinyl aromatic monomers in the random polymer block (C) of the conjugated diene copolymer (D25) is 5% by mass, the number average molecular weight is 88,000, the molecular weight distribution is 1.10, and the content of units from 1,2-bonded and / or 3,4-bonded units (vinyl bond content) is 51%.

[0643] In the conjugated diene copolymer composition (X24) obtained above, the content of vinyl aromatic monomer units in the conjugated diene copolymer (E15) is 30% by mass, the number average molecular weight is 0.6 million, the molecular weight distribution is 1.10, the content of units from 1,2-bonded and / or 3,4-bonded (vinyl bond amount) is 50%, the hydrogenation rate is 97%, and the mass ratio of conjugated diene copolymer (D25) to conjugated diene copolymer (E15) is (D25) / (E15) = 45 / 55.

[0644] (Component (II): Free radical initiator)

[0645] Perbutyl P (manufactured by NOF Corporation)

[0646] (Component (III): Curing resin)

[0647] Polyphenylene oxide (PPE) resin: OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0648] (Component (IV): Flame retardant)

[0649] SAYTEX 8010 (manufactured by ALBEMARLE)

[0650] (Composition (V): Filler)

[0651] Silicon oxide: SOC2 (manufactured by Admatechs)

[0652] [Resin composition and cured product]

[0653] <Examples 33-65>, <Comparative Examples 11-22>

[0654] Using the components (I) of the above examples and comparative examples: conjugated diene copolymers, conjugated diene copolymer compositions, and components (II) to (V) above, resin compositions and cured products were prepared.

[0655] [The preparation of varnish]

[0656] Using the conjugated diene copolymers and conjugated diene copolymer compositions from the Examples, Manufacturing Examples, and Comparative Examples, each component was measured into a container according to the proportions shown in Tables 8 to 11 below, dissolved in toluene (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred to prepare a varnish containing the resin composition.

[0657] At this point, the concentration of the resin composition in the varnish is adjusted to 40-60% by mass.

[0658] [Preparation of prepregs using varnish and the cured products of prepregs]

[0659] The varnish of the resin composition prepared according to the proportions shown in the table below was impregnated into a glass substrate (L2116, #2116 type, "L Glass", manufactured by Asahi Kasei Corporation), and then heated and dried at 130°C for 50 minutes to obtain a prepreg (PP(1)).

[0660] Six pieces of the obtained prepreg (1) were stacked and heated to 200°C at a heating rate of 2°C / min. The prepreg was heated and pressurized at 200°C for 2 hours and 3MPa to obtain a cured prepreg (cured substrate (1)) with dielectric constant, dielectric loss tangent and thickness of 0.7mm.

[0661] In addition, two PP sheets (1) were overlapped between two copper foils and heated to 200°C at a heating rate of 2°C / min. The samples for measuring copper adhesion (cured substrate (2)) were obtained under the conditions of 200°C, 60 minutes and 1.1 MPa.

[0662] [Methods for determining the physical properties of resin compositions]

[0663] ((1) Dielectric loss tangent and dielectric constant)

[0664] The dielectric loss tangent of the obtained solid substrate (1) at 10 GHz was measured using the cavity resonance method.

[0665] The measuring apparatus used was a network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resornator CP series) manufactured by Kanto Electronics Application Development Co., Ltd. For the test sample, a test piece with a width of 2.6 mm and a length of 80 mm was cut from the prepreg described in the above-described manufacturing method and the test was performed.

[0666] The Dk and Df values ​​obtained from the above measurements were evaluated in six stages according to the following criteria. Higher values ​​indicate a better dielectric loss tangent and dielectric constant.

[0667] Dk

[0668] 5: Dielectric constant is less than 3.0.

[0669] 4: Dielectric constant is less than 3.1 and greater than 3.0.

[0670] 3: Dielectric constant less than 3.3 and greater than 3.1.

[0671] 2: Dielectric constant less than 3.4 and greater than 3.3.

[0672] 1: Dielectric constant less than 3.5 and greater than 3.4.

[0673] 0: Dielectric constant is 3.5 or higher.

[0674] Df

[0675] 5: The dielectric loss tangent is less than 0.0015.

[0676] 4: The dielectric loss tangent is less than 0.0019 and greater than 0.0015.

[0677] 3: The dielectric loss tangent is less than 0.0022 and greater than 0.0019.

[0678] 2: The dielectric loss tangent is less than 0.0025 and greater than 0.0022.

[0679] 1: The tangent of the dielectric loss angle is less than 0.0027 and greater than 0.0025.

[0680] 0: The tangent of the dielectric loss angle is above 0.0027.

[0681] (2) Glass transition temperature (Tg)

[0682] The dynamic viscoelasticity of the cured substrate (1) was measured, and the temperature at which tanδ reaches its maximum was determined as the glass transition temperature (Tg).

[0683] The measuring apparatus used was ARES (trade name manufactured by TA Instruments Japan). The cured prepreg was cut into pieces with a length of 40 mm, a width of approximately 10 mm, and a thickness of 0.7 mm. Measurements were performed in a torsion mode at a frequency of 10 rad / s and a measurement temperature of -150 to 270°C.

[0684] The Tg values ​​obtained from the above measurements were evaluated in six stages according to the following criteria. Higher values ​​indicate higher Tg and better heat resistance.

[0685] 5: The glass transition temperature is above 200℃.

[0686] 4: The glass transition temperature is above 190℃ and below 200℃.

[0687] 3: The glass transition temperature is above 170℃ and below 190℃.

[0688] 2: The glass transition temperature is above 150℃ and below 170℃.

[0689] 1: The glass transition temperature is above 140℃ and below 150℃.

[0690] 0: Glass transition temperature less than 140℃.

[0691] (3) Adhesion to copper foil)

[0692] The copper adhesion of the cured substrate (2) was evaluated using a tensile compression testing machine (TGE) manufactured by Minebea Mitsumi Co., Ltd.

[0693] The adhesive strength obtained from the above measurements was evaluated in six stages according to the following criteria. A higher value indicates better adhesion to the copper foil.

[0694] 5: Copper peel strength is above 0.8 N / mm.

[0695] 4: Copper peel strength is above 0.6 N / mm and less than 0.8 N / mm.

[0696] 3: Copper peel strength is above 0.3 N / mm and less than 0.6 N / mm.

[0697] 2: Copper peel strength is above 0.2 N / mm and less than 0.3 N / mm.

[0698] 1: Copper peel strength is above 0.1 N / mm and less than 0.2 N / mm.

[0699] 0: Copper peel strength is less than 0.1 N / mm.

[0700] (4) Minimum viscosity at curing)

[0701] The melt viscosity of the PP (1) prepared in the examples and comparative examples was determined using a dynamic viscoelasticity measuring apparatus (ARES-G2, manufactured by TA Instruments Japan). The measurement was performed using parallel plates with a diameter of 8 mm, with six PP (1) sheets stacked on top of each other. The measurement conditions were set as follows: initial temperature 50°C to 250°C, heating rate 5°C / min, temperature interval 2.5°C, and vibration 1 Hz / deg. The lowest value of the obtained complex viscosity was taken as the minimum viscosity at curing.

[0702] The adhesive strength obtained from the above measurements was evaluated in four stages according to the following criteria. The smaller the value, the lower the viscosity.

[0703] 4: Below 50000 Pa·s

[0704] 3: Below 60000 Pa·s

[0705] 2: Below 300,000 Pa·s

[0706] 1: Below 1,000,000 Pa·s

[0707] 0: Exceeding 1,000,000 Pa·s

[0708] [Table 1]

[0709] [Table 2]

[0710] [Table 3]

[0711] [Table 4]

[0712] [Table 5]

[0713] [Table 6]

[0714] [Table 7]

[0715] [Table 8]

[0716] [Table 9]

[0717] [Table 10]

[0718] [Table 11]

[0719] The embodiments exhibit low dielectric constant and low dielectric loss tangent, as well as excellent heat resistance and adhesion to metal foil. Therefore, this invention is suitable for applications using cured glass cloth and printed circuit boards using metal laminates.

[0720] This application is based on Japanese patent application (Japanese Patent Application No. 2024-032298) filed with the Japan Patent Office on March 4, 2024, the contents of which are incorporated herein by reference.

[0721] Industrial applicability

[0722] The conjugated diene copolymers, resin compositions comprising the above-mentioned conjugated diene copolymers, and cured products of the present invention have industrial applicability as materials for films, prepregs, electronic circuit boards, and next-generation communication boards.

Claims

1. A conjugated diene copolymer that satisfies the following conditions (1) to (3), Condition (1): have: Polymer blocks (A) containing vinyl aromatic monomer units (a-1) with free radical reactive groups, Polymer blocks (B) mainly composed of conjugated diene monomer units (b), and A random polymer block (C) comprising the vinyl aromatic monomer unit (a-1) having a free radical reactive group and the conjugated diene monomer unit (b), and being primarily composed of the total of the vinyl aromatic monomer unit (a) comprising the unit (a-1) and the conjugated diene monomer unit (b). Condition (2): The number average molecular weight of the conjugated diene copolymer exceeds 40,000 and is less than 150,000; Condition (3): The content of all vinyl aromatic monomer units (a) containing the unit (a-1) in the conjugated diene copolymer is 5% to 70% by mass.

2. The conjugated diene copolymer according to claim 1, wherein, The conjugated diene copolymer also satisfies the following condition (4). Condition (4): The number average molecular weight of the conjugated diene copolymer exceeds 40,000 and is less than 100,000.

3. The conjugated diene copolymer according to claim 1, wherein, The polymer block (A) further comprises a vinyl aromatic monomer unit, namely unit (a-2), wherein unit (a-2) does not include unit (a-1). The polymer block (A) is mainly composed of the vinyl aromatic monomer unit (a-1) with free radical reactive groups and the vinyl aromatic monomer unit (a-2). The total content of unit (a-1) and unit (a-2) in the conjugated diene copolymer is 5% to 70% by mass. The random polymer block (C) further comprises a vinyl aromatic monomer unit, namely unit (a-2), wherein unit (a-2) does not include unit (a-1), and the random polymer block (C) is mainly composed of the sum of unit (a-1), unit (a-2) and the conjugated diene monomer unit (b).

4. The conjugated diene copolymer according to claim 1, wherein, The conjugated diene monomer unit (b) is a non-cyclic conjugated diene monomer unit.

5. The conjugated diene copolymer according to claim 1, wherein, At least a portion of the conjugated diene monomer units of the conjugated diene copolymer have been hydrogenated.

6. The conjugated diene copolymer according to claim 3, wherein, The conjugated diene copolymer also satisfies the following condition (5). Condition (5): The mass ratio of the unit (a-1) to the unit (a-2) is (a-1) / (a-2) = 30 / 70 to 99 / 1.

7. The conjugated diene copolymer according to claim 1, wherein, At least a portion of the conjugated diene monomer units of the conjugated diene copolymer have been hydrogenated to a hydrogenation rate of 98% or less.

8. The conjugated diene copolymer according to claim 1, wherein, At least a portion of the conjugated diene monomer units of the conjugated diene copolymer have been hydrogenated, with a hydrogenation rate of 50% to 98%.

9. The conjugated diene copolymer according to claim 1, wherein, The conjugated diene copolymer has three or more ends.

10. The conjugated diene copolymer according to claim 1, wherein, The conjugated diene copolymer has more than 5 ends.

11. A conjugated diene copolymer composition comprising: The conjugated diene copolymer of claim 1, namely the conjugated diene copolymer (D); and Conjugated diene copolymers (E) that satisfy conditions (6) to (7) below, Condition (6): Number average molecular weight is below 40,000; Condition (7): having at least one polymer block selected from the group consisting of polymer block (A), random polymer block (C) and polymer block (B), and having said polymer block (A) and / or said random polymer block (C), said polymer block (A) comprising a vinyl aromatic monomer unit (a-1) having a free radical reactive group, said random polymer block (C) comprising said unit (a-1) and a conjugated diene monomer unit (b), and being primarily composed of the total of the vinyl aromatic monomer unit (a) comprising said unit (a-1) and said conjugated diene monomer unit (b), said polymer block (B) being primarily composed of a conjugated diene monomer unit.

12. The conjugated diene copolymer composition according to claim 11, wherein, The polymer block (A) constituting the conjugated diene copolymer (E) further comprises a vinyl aromatic monomer unit, namely unit (a-2), wherein unit (a-2) does not include unit (a-1). The polymer block (A) constituting the conjugated diene copolymer (E) is mainly composed of the vinyl aromatic monomer unit (a-1) having a free radical reactive group and the vinyl aromatic monomer unit (a-2). The random polymer block (C) constituting the conjugated diene copolymer (E) further comprises a vinyl aromatic monomer unit, namely unit (a-2), wherein unit (a-2) does not include unit (a-1).

13. The conjugated diene copolymer composition according to claim 11, wherein, The conjugated diene copolymer (E) also satisfies the following condition (8), Condition (8): The ratio of the number-average molecular weight MnD of the conjugated diene copolymer (D) to the number-average molecular weight MnE of the conjugated diene copolymer (E), MnD / MnE, is greater than 2.

14. A resin composition comprising: Component (I): the conjugated diene copolymer of any one of claims 1 to 10, or the conjugated diene copolymer composition of any one of claims 11 to 13; and At least one component is selected from the group consisting of components (II) to (III) below. Component (II): Free radical initiator; Component (III): Curing resin, wherein, Excluding ingredient (I).

15. The resin composition according to claim 14, wherein, The component (III) is a free radical curable resin, and is a curable resin having at least one reactive group selected from the group consisting of vinyl, maleimide, allyl and methacryloyl groups as reactive groups.

16. The cured product of the conjugated diene copolymer according to any one of claims 1 to 10.

17. The cured product of the conjugated diene copolymer composition according to any one of claims 11 to 13.

18. The cured product of the resin composition of claim 14.

19. A resin film comprising the resin composition of claim 14.

20. A prepreg, which is a composite of a substrate and the resin composition of claim 14.

21. The prepreg according to claim 20, wherein, The substrate is glass cloth.

22. A laminate having the resin film and metal foil as described in claim 19.

23. A material for an electronic circuit board comprising the cured material of claim 18.

24. A material for an electronic circuit board comprising the resin film of claim 19.

25. A material for an electronic circuit board comprising the prepreg as described in claim 20.

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