Block copolymer, and resin composition and cured product containing the same

Abstract

The present invention relates to a modified block copolymer, which is a copolymer having a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound, containing 0.01 mass% or more of a polar group, satisfying <Condition (i)> the total amount of the polymer block (A) mainly composed of a vinyl aromatic compound in the modified block copolymer is 35 mass% or more; <Condition (ii)> the total content of Co, Ti, Ni and Li is 90 ppm or less; and <Condition (iii)> the weight average molecular weight is 35,000 to 11.5,000, a resin composition containing the modified block copolymer, and a cured product.

Description

Technical Field

[0001] This invention relates to block copolymers and resin compositions and cured products containing such block copolymers. Background Technology

[0002] In recent years, with the significant advancements in information network technology and the expansion of information network services, electronic devices are demanding larger information capacities and higher processing speeds. To meet these requirements, materials with low dielectric loss are being sought in substrate materials such as printed circuit boards and flexible substrates. For such materials, to reduce dielectric loss, resin-cured products using thermosetting resins such as epoxy resins or thermoplastic resins such as polyphenylene ether resins as the main component have been studied. However, there is still room for improvement in the low dielectric constant and low dielectric loss tangent of these resin-cured products, and the information capacity and processing speed are sometimes limited.

[0003] Therefore, in order to improve this problem, various solutions have been proposed, such as adding rubber components to the above-mentioned resin composition and curing products with rubber components as the main component. However, with the addition of rubber components, the low dielectric constant and low dielectric loss tangent result in reduced adhesion and strength to the metal foil (especially copper foil) used as the substrate.

[0004] Furthermore, in flexible printed circuit boards, adhesives are typically used for bonding with thermosetting resins and / or metal foils. These adhesives maintain strong adhesion to the thermosetting resins of the organic insulating layer and / or the metal foils of the substrate conductor. With the increasing capacity of information and the higher processing speeds, achieving low dielectric constants, low dielectric loss tangents, and high strength, similar to those of the substrate material, has become a challenge.

[0005] For example, in Patent Document 1, in order to achieve low dielectric loss tangent, low dielectric constant, and improved adhesion to metal foil and / or thermosetting resin of epoxy resin composition, an elastomer comprising at least a nitrile rubber containing carboxyl groups is disclosed.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2008 / 136096 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, the resin composition disclosed in Patent Document 1 is still not sufficiently low in terms of dielectric loss tangent and dielectric constant, and has the problem of reduced strength of the cured product and reduced adhesion to metal foil and / or thermosetting resin due to the addition of modifier.

[0011] Therefore, in view of the above, the object of the present invention is to provide a modified block copolymer that can achieve a cured product with low dielectric constant, low dielectric loss tangent and high strength while maintaining adhesion to metal foil (especially copper foil) and / or to thermosetting resin (especially polyimide resin) of organic insulating layer.

[0012] Methods for solving problems

[0013] In order to solve the problems of the prior art, the inventors conducted in-depth research and found that modified block copolymers containing specified structures and polar groups and meeting specified conditions have excellent adhesion to metal foils and / or thermosetting resins, can maintain strength in the cured product, and are excellent in terms of low dielectric constant and low dielectric loss tangent, thus completing the present invention.

[0014] That is, the present invention is as follows. [1]

[0016] A modified block copolymer is a copolymer having polymer blocks (A) mainly composed of vinyl aromatic compounds and polymer blocks (B) mainly composed of conjugated diene compounds, wherein,

[0017] The copolymer contains more than 0.01% by mass of polar groups.

[0018] The following conditions (i) to (iii) must be met:

[0019] <Condition (i)>

[0020] The total amount of polymer blocks (A) mainly composed of vinyl aromatic compounds in the above modified block copolymer is 35% by mass or more;

[0021] <Condition(ii)>

[0022] The total content of Co, Ti, Ni and Li is below 90 ppm;

[0023] <Condition (iii)>

[0024] The weight-average molecular weight is 35,000 to 115,000. [2]

[0026] The modified block copolymer as described in [1], wherein the modified block copolymer is hydrogenated. [3]

[0028] The modified block copolymer as described in [1] or [2], wherein when the amount of the 1,2-linked and / or 3,4-linked units (a) in the polymer block (B) is set to 100%, the amount of the hydrogenated alkenyl monomer units (a1) of the unit (a) is 80% or more. [4]

[0030] The modified block copolymers described in [3], wherein,

[0031] The polymer block (B) comprises the alkenyl monomer unit (a1) and a hydrogenated alkenyl monomer unit (b1) derived from the 1,4-linked unit (b).

[0032] When the total content of the polymer block (B) is set to 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) is 90% or more. [5]

[0034] The modified block copolymer as described in any one of [1] to [4], wherein the polar group is bonded to the polymer block (B). [6]

[0036] The block copolymer as described in any one of [1] to [5], wherein the polar group is at least one selected from the group consisting of carboxyl, dicarboxyl and anhydride groups. [7]

[0038] A resin composition comprising:

[0039] Component (I): the modified block copolymer described in any one of [1] to [6]; and

[0040] Choose at least one from the group consisting of components (II) to (IV) below.

[0041] Component (II): Free radical initiator;

[0042] Component (III) Polar resin (excluding component (I));

[0043] Component (IV) Curing agent (excluding component (II)). [8]

[0045] The resin composition as described in [7], wherein the above component (III) is at least one resin selected from the group consisting of epoxy resins, polyimide resins, polyphenylene ether resins, liquid crystal polyester resins and fluorinated resins. [9]

[0047] The resin composition as described in [7] or [8], wherein the above component (III) is an epoxy resin.

[10]

[0049] A cured product comprising any one of the modified block copolymers described in [1] to [6].

[11]

[0051] An adhesive comprising any one of the modified block copolymers described in [1] to [6].

[12]

[0053] A cured product, which is a cured product of the resin composition described in any one of [7] to [9].

[13]

[0055] An adhesive comprising any one of the resin compositions described in [7] to [9].

[14]

[0057] A resin film comprising any one of the resin compositions described in [7] to [9].

[15]

[0059] A prepreg is a composite of a substrate and a resin composition described in any one of [7] to [9].

[16]

[0061] The prepreg as described in

[15] , wherein the substrate is glass cloth.

[17]

[0063] A laminate is formed by laminating a cured resin composition of any one of [7] to [9] and / or a prepreg described in

[15] or

[16] with a metal foil and / or a thermosetting resin.

[18]

[0065] The laminate as described in

[17] , wherein the metal foil is copper foil and the thermosetting resin is a polyimide resin.

[19]

[0067] A laminate is formed by laminating a cured resin composition of any one of [7] to [9] and / or a cured prepreg of any one of

[15] or

[16] with a metal foil.

[20]

[0069] An electronic circuit board material comprising the cured material described in

[10] or

[12] .

[0070] The effects of the invention

[0071] The modified block copolymer of the present invention exhibits excellent adhesion to metal foil and to the thermosetting resin constituting the organic insulating layer, resulting in a cured product with high strength, low dielectric constant, and low dielectric loss tangent. Detailed Implementation

[0072] The specific embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail below.

[0073] 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.

[0074] (1) Modified block copolymers

[0075] The modified block copolymer of this embodiment is a copolymer having polymer blocks (A) mainly composed of vinyl aromatic compounds and polymer blocks (B) mainly composed of conjugated diene compounds, and contains more than 0.01% by mass of polar groups.

[0076] The following conditions (i) to (iii) must be met.

[0077] <Condition (i)>

[0078] The total amount of polymer blocks (A) mainly composed of vinyl aromatic compounds in the above modified block copolymer is 35% by mass or more.

[0079] <Condition(ii)>

[0080] The total content of Co, Ti, Ni and Li is below 90 ppm.

[0081] <Condition (iii)>

[0082] The weight-average molecular weight is 35,000 to 115,000.

[0083] The modified block copolymer of this embodiment has the following characteristics: excellent adhesion to metal foil and / or thermosetting resin, maintains strength in the cured product, and excels in low dielectric constant and low dielectric loss tangent.

[0084] Conjugated dienes are dienes that have a pair of conjugated double bonds.

[0085] 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, and 1,3-cyclohexadiene. Among these, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred. 1,3-butadiene and isoprene are widely used, readily available, cost-effective, and readily copolymerized with styrene, which is widely used as a vinyl aromatic compound.

[0086] These substances can be used alone or in combination of two or more.

[0087] In addition, the aforementioned conjugated diene compounds can also be compounds of biological origin.

[0088] In this specification, the conjugated diene compound unit refers to the structural unit derived from the conjugated diene compound in the polymer formed by the polymerization of the conjugated diene compound.

[0089] Examples of vinyl aromatic compounds include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, etc.

[0090] These substances can be used alone or in combination of two or more.

[0091] In this specification, a vinyl aromatic compound unit refers to a structural unit derived from a vinyl aromatic compound in a polymer formed by the polymerization of a vinyl aromatic compound.

[0092] The modified block copolymer of this embodiment is a modified block copolymer having a polymer block (A) mainly composed of vinyl aromatic compound units and a polymer block (B) mainly composed of conjugated diene compound units.

[0093] The polymer blocks (A) constituting the modified block copolymer (hereinafter also referred to as "component (I)") of this embodiment are mainly composed of vinyl aromatic compounds.

[0094] Here, "as the main body" means that the total mass of the vinyl aromatic compound unit relative to the polymer block (A) is more than 70% by mass.

[0095] The content of vinyl aromatic compound units in the polymer block (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass relative to the total mass of the polymer block (A) (without intentionally adding other monomers).

[0096] The polymer blocks (B) constituting component (I) are mainly composed of conjugated diene compounds.

[0097] Here, "as the main body" means that, from the perspective of curability, the total mass of the conjugated diene compound unit relative to the polymer block (B) is more than 70% by mass.

[0098] The content of conjugated diene compound units in polymer block (B) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass relative to the total mass of polymer block (B). If a polymer block containing conjugated diene compound units also contains vinyl aromatic compound units, it is classified as polymer block (B) if the content of conjugated diene compound units is 70% by mass or more; otherwise, it is classified as polymer block (C).

[0099] Regarding the content of polymer blocks (A) in component (I), the unhydrogenated block copolymer or the hydrogenated block copolymer can be used as the analyte and determined by nuclear magnetic resonance (NMR) (the method described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981). Hereinafter referred to as "NMR method").

[0100] Component (I) can be a block copolymer with polymer blocks (A) and polymer blocks (B) as basic backbones and these basic backbones having repeating structures.

[0101] In addition, the modified block copolymer of this embodiment may have polymer blocks (C) composed of copolymers of vinyl aromatic compounds and conjugated diene compounds.

[0102] The vinyl aromatic compounds and conjugated diene compounds used to form the vinyl aromatic monomer units and conjugated diene monomer units contained in the polymer block (C) can be compounds that can be used in the polymer blocks (A) and (B).

[0103] There are no particular limitations on the distribution of vinyl aromatic monomer units in the polymer block (C) described above. The vinyl aromatic monomer units in the random copolymer block (c) can be uniformly distributed or gradually distributed. In addition, there can be multiple uniformly distributed portions and / or gradually distributed portions of the vinyl aromatic monomer units, or there can be multiple segments with different contents of vinyl aromatic monomer units.

[0104] Other compounds capable of copolymerizing with conjugated diene compounds and vinyl aromatic compounds may also be used in the modified block polymers of this embodiment.

[0105] The structure of the modified block copolymer in this embodiment is not particularly limited; for example, substances having the structure represented by the following formula can be cited.

[0106] (ab)n, b-(ab)n, a-(ba)n, (ab)mX, (ba)mX, [(ab)n]mX, [(ba)n]mX, [b-(ab)n]mX, [a-(ba)n]mX, [(ab)na]mX, [(ba)nb]mX,

[0107] c-(ba)n, c-(ab)n,

[0108] c-(aba)n, c-(bab)n,

[0109] ac-(ba)n、ac-(ab)n、

[0110] ac-(ba)nb、[(abc)n]mX、

[0111] [a-(bc)n]mX、[(ab)nc]mX、

[0112] [(aba)nc]mX、

[0113] [(bab)nc]mX、[(cba)n]mX、

[0114] [c-(ba)n]mX, [c-(aba)n]mX, [c-(bab)n]mX

[0115] a-(bc)n、a-(cb)n、

[0116] a-(cbc)n, a-(bcb)n,

[0117] ca-(bc)n、ca-(cb)n、

[0118] ca-(bc)nb、[(cba)n]mX、

[0119] [c-(ba)n]mX、[(cb)na]mX、

[0120] [(cbc)na]mX、

[0121] [(bcb)na]mX、[(abc)n]mX、

[0122] [a-(bc)n]mX, [a-(cbc)n]mX, [a-(bcb)n]mX

[0123] b-(ac)n、b-(ca)n、

[0124] b-(cac)n、b-(aca)n、

[0125] cb-(ac)n、cb-(ca)n、

[0126] cb-(ac)na、[(cab)n]mX、

[0127] [c-(ab)n]mX、[(ca)nb]mX、

[0128] [(cac)nb]mX、

[0129] [(bcb)nb]mX、[(bac)n]mX、

[0130] [b-(ac)n]mX, [b-(cac)n]mX, [b-(aca)n]mX

[0131] It should be noted that in the above general formulas, a represents the polymer block (A), b represents the polymer block (B), and c represents the copolymer block of the conjugated diene compound and the vinyl aromatic compound (polymer block (C)).

[0132] n is an integer greater than or equal to 1, preferably an integer between 1 and 5.

[0133] m is an integer greater than or equal to 2, preferably an integer between 2 and 11.

[0134] X represents a residue of a coupling agent or a residue of a multifunctional initiator.

[0135] The modified block copolymer of this embodiment is a modified block copolymer containing 0.01% by mass or more of polar groups. By containing 0.01% by mass or more of polar groups, the modified block copolymer of this embodiment exhibits excellent adhesion to metal foils and thermosetting resins. Furthermore, components (II), (III), and (IV), described later, are known to possess polar groups. The modified block copolymer of this embodiment, by containing 0.01% by mass or more of polar groups, demonstrates improved compatibility with components (II), (III), and (IV), resulting in improved strength of the cured product containing the modified block copolymer of this embodiment, and optimized dielectric loss tangent and dielectric constant.

[0136] A "polar group" is an atomic group in which there is a charge shift between covalently bonded atoms.

[0137] In covalent bonds between dissimilar atoms such as carbon-oxygen, carbon-nitrogen, carbon-halogen, oxygen-hydrogen, nitrogen-hydrogen, and silicon-hydrogen, charge shifts occur due to the difference in electronegativity of each atom. Therefore, atomic groups that typically contain heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, and halogens exhibit polarity.

[0138] In the modified block copolymer of this embodiment, from the perspective of adhesion to metal foil and thermosetting resin, the addition amount (content) of the polar groups is preferably 0.01% to 10% by mass, more preferably 0.01% to 8.0% by mass, further preferably 0.05% to 6.0% by mass, even more preferably 0.05% to 5.0% by mass, and even more preferably 0.05% to 4% by mass.

[0139] According to the inventors' understanding, when the amount of addition of polar groups is 10% by mass or less, the properties of compositions containing modified block copolymers, cured products, and multilayers of metal foils can be improved, and when attempting to produce modified block copolymers of 10% by mass or less, side reactions such as crosslinking can be suppressed during modification.

[0140] From the perspective of suppressing side reactions in the modification process and suppressing gel formation, it is preferable to make the amount of polar group addition 10% by mass or less. By suppressing byproducts and / or gel, when resin compositions, cured products, and multilayers with metal foils are prepared by mixing with components (II), (III), and (IV) described later, there is a tendency for them to easily exhibit sufficient strength.

[0141] Examples of "polar groups" 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.

[0142] In particular, as a polar group, from the perspective of adhesion to the metal foil mentioned above, it is more preferable to have a functional group having at least one functional group selected from the group consisting of anhydride, carboxyl, dicarboxyl, anhydride, and amino. From the perspective of storage stability, it is even more preferable to have at least one functional group selected from the group consisting of carboxyl, dicarboxyl, and anhydride. In the polar group formation process, when an anhydride is attached to the block copolymer, moisture in the air may react with the anhydride, and a portion of it may be converted into a carboxylic acid group, but the amount is not particularly limited. That is, in this specification, "at least one functional group selected from the group consisting of anhydride, carboxylic acid, and hydroxyl" includes the following manner: in the modification process, after the anhydride group is added as a polar group, the anhydride actively or unintentionally undergoes hydration, changing into a carboxylic acid group or a hydroxyl group.

[0143] In the modified block copolymer of this embodiment, when the polar group is an amino group, from the perspective of storage stability, the amount of amino addition is preferably 0.01% to 5% by mass, more preferably 0.01% to 1% by mass, further preferably 0.01% to 0.8% by mass, and even more preferably 0.01% to 0.5% by mass.

[0144] It should be noted that, in this embodiment, the amount (content) of the addition of polar groups can be determined by the method described in the examples below.

[0145] The polar groups can be formed using compounds (sometimes referred to below as modifiers) that can react with the active ends during the polymerization of block copolymers and / or the post-polymerized vinyl aromatic compounds and / or conjugated diene compounds.

[0146] Examples of modifiers include, but are not limited to, tetraglycidyl-m-phenylenediamine, tetraglycidyl-1,3-diaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidyloxyethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyldimethylphenoxysilane, bis(γ-glycidyloxypropyl)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.

[0147] As a method for incorporating polar groups into the modified block copolymer of this embodiment, any known method can be used, and there is no particular limitation. Examples include melt blending and methods of reacting by dissolving or dispersing the components in a solvent or the like. Additionally, methods such as polymerization using anionic living polymerization with a polymerization initiator having functional groups and an unsaturated monomer having functional groups, methods of forming functional groups at active ends, and methods of subjecting a modifier containing functional groups to an addition reaction can also be used, but melt blending is preferred.

[0148] Other methods for forming "polar groups" in the modified block copolymer of this embodiment are not particularly limited, and examples include reacting an organolithium compound or other organoalkali metal compound with the block copolymer (metallization reaction), or causing a modifier with functional groups to undergo an addition reaction with the block polymer containing organoalkali metals.

[0149] In the modified block copolymer of this embodiment, the polar groups are preferably combined with the polymer block (B).

[0150] The bonding of polar groups to polymer blocks (B) refers to the state in which polar groups are bonded to the double bonds contained in polymer blocks (B) through an addition reaction. In polymer blocks (B), double bonds from conjugated dienes are also present after hydrogenation. Modified block copolymers containing polar groups can be obtained by implementing methods such as blending compounds with polar groups to the block copolymer during the melt blending process.

[0151] When the polymer block (B) is present at the end of the block copolymer, the polymer block (B) also has polar groups when a polymerization initiator with functional groups is reacted or when a modifier containing functional groups at the active end of the block copolymer is reacted. However, in this embodiment, the state in which such polar groups are combined with the terminal conjugated diene compound unit is not included.

[0152] By combining the "polar groups" with the polymer blocks (B) of the block copolymer, not only can the adhesion to the metal foil be improved, but also the compatibility with the polar resin of component (III) described later can be improved, and there is a tendency to obtain resin compositions, cured products, adhesives, multilayers of metal foil, and prepregs with excellent heat resistance.

[0153] Methods for confirming the binding site of "polar groups" include analysis using a nuclear magnetic resonance apparatus; and determination of residual double bonds in polymer blocks (B) by appropriate methods, such as matrix-assisted laser desorption / ionization.

[0154] The modified block copolymer of this embodiment satisfies the following conditions (i), (ii) and (iii).

[0155] <Condition (i)>

[0156] The total amount of polymer blocks (A) mainly composed of vinyl aromatic compounds in the above modified block copolymer is 35% by mass or more.

[0157] Polymers composed of vinyl aromatic compounds are known to be amorphous. In the modified block copolymer of this embodiment, by making the total amount of polymer blocks (A) mainly composed of vinyl aromatic compounds 35% by mass or more, the vinyl aromatic compounds aggregate and entangle in the resin composition and / or cured product described later. Therefore, the strength of the resin composition containing the above-mentioned block copolymer, the cured product composed of the resin composition, and the multilayer and / or prepreg of the above-mentioned block copolymer and / or resin composition and / or cured product containing the above-mentioned block copolymer with the metal foil is improved, and the dielectric loss tangent and dielectric constant are optimized. In addition, from the perspective of solubility parameters, vinyl aromatic compounds interact more strongly with the metal foil and thermosetting resin as the substrate than conjugated diene compounds. Therefore, in the modified block copolymer of this embodiment, by making the total amount of polymer blocks (A) mainly composed of vinyl aromatic compounds 35% by mass or more, the adhesion is improved.

[0158] From the above perspective, the total amount of polymer blocks (A) mainly composed of vinyl aromatic compounds in the modified block copolymer of this embodiment is preferably 35% by mass or more, and from the perspective of improving the strength, it is more preferably 37% by mass or more, further preferably 40% by mass or more, especially preferably 43% by mass or more, and particularly preferably 45% by mass or more. There is no particular upper limit, but from the perspective of containing 0.01% by mass or more of polar groups, it is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, especially preferably 80% by mass or less, and particularly preferably 75% by mass or less.

[0159] The total amount of polymer blocks (A) in the modified block copolymer, which are mainly composed of vinyl aromatic compounds, can be controlled within the above-mentioned numerical range by adjusting the amount of monomer added, the timing of addition, polymerization temperature, and other polymerization conditions. It can be calculated by the method described in the examples below.

[0160] Since polymer block (A) is a vinyl aromatic compound-based polymer block, it is known to be amorphous. Conjugated diene compound units are known to have the function of curing the above-mentioned block copolymer individually and / or with components (III) and (IV) described later. The conjugated diene compound units, individually and / or with components (III) and (IV), form a bridging structure to obtain a cured product. The strength is increased by the close intertwining of unreacted block copolymer polymer blocks (A) with each other, where the polymer blocks (A) are primarily composed of vinyl aromatic compounds.

[0161] <Condition(ii)>

[0162] The total content of Co, Ti, Ni, and Li in the modified block copolymer of this embodiment is less than 90 ppm. This content is a mass ratio, that is, it refers to ppm by mass. The same applies in this specification.

[0163] In the block copolymer manufacturing method described later, compounds containing metal atoms, such as polymerization initiators used in the anionic living polymerization process, compounds containing metal atoms in the hydrogenation catalyst included in the hydrogenation reaction described later, and / or compounds generated by reacting moisture in the air with metal atoms through a solvent removal process during polymerization, may remain in the block copolymer. Condition (ii) above specifies an upper limit for the content of such compounds, particularly compounds containing Ti, Ni, Li, and Co.

[0164] There are no particular limitations on such compounds containing Ti, Ni, Li, and Co. Examples include oxides of various atoms such as titanium oxide, amorphous titanium oxide, orthotitanic acid, metatitanic acid, titanium hydroxide, nickel hydroxide, nickel monoxide, lithium oxide, lithium hydroxide, cobalt oxide, and cobalt hydroxide, as well as composite oxides of various atoms and dissimilar metals such as lithium titanate, barium titanate, strontium titanate, nickel titanate, and nickel-iron oxide.

[0165] Here, the metal atom conversion is typically obtained by converting the residual weight of the compound containing the aforementioned metal atoms in the block copolymer into the mass per unit metal atom using the molecular weight of the compound. It should be noted that while the method described above can be used to calculate this if the compound containing the aforementioned metal atoms can be identified, such identification is difficult in most cases. In such cases, the metal atom conversion value of the total content of Ti, Ni, Li, and Co relative to the total amount of the block copolymer can be determined using the method described in the later examples. That is, in condition (ii), the metal atom conversion value of the total content of Ti, Ni, Li, and Co can be the sum of the measured values ​​of these metal atoms when performing ICP elemental analysis on the block copolymer.

[0166] By keeping the residual amounts of Ti, Ni, Li, and Co in the block copolymer below 90 ppm (converted to metal atoms, hereinafter also referred to as "metal content"), it is possible to maintain the thermal stability of the modified block copolymer, suppress the formation of gel components when polar groups are combined with the block copolymer through the above-mentioned melt mixing, and improve the storage stability of the resin composition described later in the varnish state.

[0167] The detailed mechanism of this phenomenon is unclear, but it can be speculated, for example, as follows, but is not limited to this. It is generally known that when a polymer is exposed to high temperatures, carbon free radicals are generated, which react with oxygen in the air to generate hydrogen peroxide. In the presence of the aforementioned metal compound, under the above conditions, the decomposition of free radicals based on redox reactions is promoted, and / or the hydrogenated block copolymer itself reacts with the aforementioned metal compound to generate free radicals. In addition, metal ions from the aforementioned metal compound form charge-transfer complexes and / or reactive oxygen species with oxygen in the air, which react with the hydrogenated block copolymer to generate carbon free radicals. When the amount of the aforementioned metal is high, although not limited to the above reaction mechanism, active species such as carbon free radicals and / or hydrogen peroxide are easily generated in the block copolymer through the above reaction mechanism, etc. If a large amount of such active species is generated, the hydrogenated block copolymer is prone to bonding with each other, the gel content increases, and the adhesion to the metal foil, the dielectric constant decreases, the dielectric loss tangent decreases, and the strength deteriorates.

[0168] Furthermore, in electronic material applications, if the metal content is 90 ppm or less, the resin composition containing the modified block copolymer of this embodiment and the cured product composed of the resin composition, the multilayer of the modified block copolymer of this embodiment and / or the resin composition containing the modified block copolymer of this embodiment and / or the cured product and the metal foil, and the prepreg not only improve the dielectric constant and dielectric loss tangent, but also suppress ion migration.

[0169] In the modified block copolymer of this embodiment, the metal content is preferably 85 ppm or less, more preferably 80 ppm or less, further preferably 70 ppm or less, and particularly preferably 60 ppm or less.

[0170] As a method to reduce the metal content to 90 ppm or less, existing known methods can be used without particular limitation. For example, a method can be used to neutralize the hydrogenation catalyst residue by adding water and carbon dioxide after the hydrogenation reaction of the block copolymer; or a method can be used to neutralize the hydrogenation catalyst residue by adding acid in addition to water and carbon dioxide. More specifically, the method described in International Patent Publication No. 2014 / 112411 (Japanese Patent Application No. 2014-557427) can be cited as an example. Even with these removal methods, water containing hydroxide of the metal compound will be mixed into the desolventizing process of the hydrogenated block copolymer, typically containing about 1 to 15 ppm of metal. Therefore, in the modified block copolymer of this embodiment, it is preferable to remove 20% of the metal added during manufacturing, more preferably 30%, further preferably 40%, particularly preferably 50%, and even more particularly preferably 60%. Alternatively, the amounts of polymerization initiator and hydrogenation catalyst can be reduced. However, if the amount of polymerization initiator is reduced, the molecular weight of the block copolymer increases, falling outside the preferred molecular weight range described later, thus tending to reduce processability. Furthermore, if the amount of catalyst in the hydrogenation reaction is reduced, the hydrogenation reaction time required to achieve the preferred hydrogenation rate range described above becomes longer, and / or the hydrogenation reaction temperature increases, thus tending to significantly reduce productivity.

[0171] <Condition (iii)>

[0172] The modified block copolymer of this embodiment has a weight-average molecular weight of 35,000 to 115,000.

[0173] The weight-average molecular weight of the modified block copolymer can be determined by the method described in the following examples, and the weight-average molecular weight (Mn) is obtained as follows: based on a calibration curve obtained from the determination of commercially available standard polystyrene (using the peak molecular weight of standard polystyrene), the molecular weight of the peak in the chromatogram obtained by gel permeation chromatography (GPC) is determined, thereby obtaining the weight-average molecular weight (Mn).

[0174] By having a weight-average molecular weight of 35,000 or more for the modified block copolymer of this embodiment, the adhesion strength in the cured product containing the modified block copolymer, the resin composition containing the modified block copolymer, and the multilayer of the metal foil is improved. In the modified block copolymer of this embodiment, by having a weight-average molecular weight of 115,000 or less, shear exothermics can be suppressed when polar groups are combined with the block copolymer during melt mixing, preventing the formation of gel components. This improves the adhesion, strength, dielectric constant, and dielectric loss tangent in the multilayer of the cured product containing the resin composition containing the modified block copolymer and the metal foil.

[0175] Based on the above, the weight-average molecular weight of the modified block copolymer is preferably 35,000 to 110,000, more preferably 35,000 to 100,000, further preferably 35,000 to 95,000, and particularly preferably 35,000 to 90,000.

[0176] The molecular weight distribution is the ratio of weight-average molecular weight (Mw) to weight-average molecular weight (Mn), Mw / Mn.

[0177] The molecular weight distribution of the modified block copolymer of this embodiment, as determined by GPC, is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and even more preferably 2.5 or less.

[0178] The weight-average molecular weight of the modified block copolymer in this embodiment is preferably 35,000 or more and 115,000 or less.

[0179] The polymer block (B) in the modified block copolymer of this embodiment preferably comprises units (a) from 1,2-bonded and / or 3,4-bonded, and units (b) from 1,4-bonded. When the total content of the polymer block (B) is set to 100%, from the perspective of the reactivity of the block copolymer with each other and / or with components (III) and (IV) described later during curing, the content of units (a) from 1,2-bonded and / or 3,4-bonded is preferably 10-95%, more preferably 15-90%, further preferably 20-85%, and particularly preferably 25-80% or less.

[0180] The content of the above-mentioned unit (a) can be controlled by the use of modifiers such as polar compounds during polymerization, and can be calculated using the methods described in the examples below.

[0181] There are no particular limitations on the modifier; for example, tertiary amine compounds or ether compounds can be mentioned, with tertiary amine compounds being preferred.

[0182] Tertiary amine compounds are compounds with the general formula R1R2R3N (where R1, R2, and R3 are hydrocarbon groups with 1 to 20 carbon atoms or hydrocarbon groups having a tertiary amino group).

[0183] 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.

[0184] The amount of regulator is preferably 0.1 mol or more, more preferably 0.5 mol or more, and more preferably 1.0 mol or more, relative to 1 mol of polymerization initiator described later.

[0185] The modified block copolymer of this embodiment is preferably hydrogenated. Furthermore, in the modified block copolymer of this embodiment, when the amount of 1,2-bonded and / or 3,4-bonded units (a) in the polymer block (B) is set to 100%, the amount of hydrogenated alkenyl monomer units (a1) of the aforementioned units (a) is preferably 80% or more. By hydrogenating the modified block copolymer, the storage stability of the resin composition described later in the varnish state before curing tends to improve, and by making the amount of unit (a1) (hereinafter also referred to as "vinyl hydrogenation rate") 80% or more, there is a tendency to further improve the storage stability. As the vinyl hydrogenation rate, it is further preferably 83% or more, more preferably 85% or more, and particularly preferably 87% or more. Furthermore, based on the above aspects, the polymer block (B) comprises an alkenyl monomer unit (a1) and an alkenyl monomer unit (b1) hydrogenated from a 1,4-linked unit (b). When the total content of the polymer block (B) is set to 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) (hereinafter also referred to as "total hydrogenation rate") is preferably 90% or more, more preferably 92% or more, further preferably 93% or more, and particularly preferably 94% or more.

[0186] There are no particular limitations on the method for hydrogenating block copolymers; conventionally known methods can be used.

[0187] There are no particular limitations on hydrogenation catalysts. For example, the following can be used: (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; (3) so-called homogeneous hydrogenation catalysts such as organometallic compounds of Ti, Ru, Rh, and Zr.

[0188] Specifically, as a hydrogenation catalyst, the hydrogenation catalysts described in, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 2-9041 may be used without particular limitation.

[0189] Preferred hydrogenation catalysts include cyclopentadiene titanium compounds and / or reducing organometallic compounds.

[0190] There are no particular limitations on the cyclopentadiene titanium compound; for example, compounds described in Japanese Patent Application Publication No. 8-109219 may be used. There are also no particular limitations on the cyclopentadiene titanium compound; examples include dicyclopentadiene titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride, which are compounds having at least one ligand with a (substituted) cyclopentadiene skeleton, an indenyl skeleton, or a fluorenyl skeleton. In the cyclopentadiene titanium compound, the aforementioned skeleton may consist of one type alone or in combination of two types.

[0191] There are no particular limitations on reducing organometallic compounds; examples include organolithium and other organoalkali metal compounds, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds. These substances can be used alone or in combination of two or more.

[0192] The hydrogenation rate can be controlled by adjusting the reaction temperature, reaction time, hydrogen supply, and catalyst amount in the hydrogenation method as needed. Regarding the temperature of 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. The pressure of the hydrogen used in the hydrogenation reaction is preferably 0.1–15 MPa, more preferably 0.2–10 MPa, and even more preferably 0.3–5 MPa. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.

[0193] Hydrogenation can be carried out using batch processes, continuous processes, or combinations thereof.

[0194] (2) Method for manufacturing modified block copolymers

[0195] Block copolymers (I) can be obtained by, but are not particularly limited to, living anionic polymerization using, for example, in hydrocarbon solvents, polymer initiators such as organoalkali metal compounds.

[0196] There are no particular limitations on what can be used as a hydrocarbon solvent. Examples include 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.

[0197] There are no particular limitations on which compounds can be used as polymerization initiators; for example, aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organoamine alkali metal compounds, which are generally known to have anionic polymerization activity for conjugated dienes and vinyl aromatic compounds, can be cited. There are also no particular limitations on which alkali metals can be used; for example, lithium, sodium, and potassium can be cited.

[0198] There are no particular limitations on the organic alkali metal compounds. Examples 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 two or more lithium atoms in one molecule.

[0199] As organoalkali metal compounds, examples 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 with sec-butyllithium, and the reaction product of divinylbenzene with sec-butyllithium and a small amount of 1,3-butadiene. Furthermore, examples include, but are not limited to, 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; and amino lithiums such as alkyl lithiums containing amino groups, diisopropylamine lithium, and hexamethyldisilazine lithium disclosed in U.S. Patent 5,527,753.

[0200] As a method for polymerizing vinyl aromatic compounds and conjugated diene polymers using organoalkali metal compounds as polymerization initiators, existing known methods can be applied.

[0201] There are no particular limitations on the polymerization method; for example, it can be batch polymerization, continuous polymerization, or any combination thereof. Batch polymerization is particularly suitable for obtaining copolymers with excellent heat resistance. The polymerization temperature is preferably 0°C to 180°C, more preferably 30°C to 150°C. The polymerization time, depending on the conditions, is preferably within 48 hours, more preferably 0.1 to 10 hours. Furthermore, an inert gas atmosphere such as nitrogen is preferred for the polymerization system. Regarding the polymerization pressure, it is not particularly limited as long as it is set within the pressure range that can maintain the monomer and solvent in the liquid phase within the above temperature range. In addition, care should be taken to avoid introducing impurities such as water, oxygen, and carbon dioxide into the polymerization system, which could deactivate the catalyst and active polymer.

[0202] In addition, at the end of the above polymerization process, a necessary amount of 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, particularly preferably 20% or less, and especially preferably does not contain a coupling agent.

[0203] As a difunctional coupling agent, any existing known substances can be used, without particular limitations.

[0204] 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; dihalo compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, and dimethyldibromosilane; and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.

[0205] Furthermore, any known substances can be used as multifunctional coupling agents with three or more functions, without particular limitation. Examples of multifunctional coupling agents with three or more functions include polyols with three or more carbon atoms; epoxidized soybean oil, diglycidyl bisphenol A, 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane, and other polycyclic epoxy compounds; silicon halide compounds represented by the general formula R4-nSiXn (where R represents a hydrocarbon group with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4); tin halide compounds represented by the general formula R4-nSnXn (where R represents a hydrocarbon group with 1 to 20 carbon atoms, X represents a halogen, and n represents an integer of 3 to 4), such as methyltrichlorosilane, tert-butyltrichlorosilane, silicon tetrachloride, and their bromides; and polycyclic halides such as methyltin trichloride, tert-butyltin trichloride, and tin tetrachloride. Alternatively, dimethyl carbonate, diethyl carbonate, etc. can also be used.

[0206] The block copolymer (I) solution obtained as described above can be purified by removing catalyst residues as needed, and the block copolymer (I) can be separated from the solution. Compounds containing the metal atoms contained in the polymerization initiator during anionic active polymerization, the hydrogenation catalyst in the hydrogenation reaction described above, and / or compounds containing the metal generated by reaction with moisture in the air during the solvent removal process of polymerization, tend to remain in the modified block copolymer of component (I). If these compounds are included in the cured product, they tend to have increased dielectric constant and dielectric loss tangent, and / or are prone to ion migration in electronic material applications. The metal compound remaining is not particularly limited to the metal contained in the polymerization initiator or the hydrogenation catalyst during hydrogenation; examples include oxides of various atoms such as titanium oxide, amorphous titanium oxide, orthotitanic acid, metatitanic acid, titanium hydroxide, nickel hydroxide, nickel monoxide, lithium oxide, lithium hydroxide, cobalt oxide, and cobalt hydroxide; and composite oxides of various atoms of lithium titanate, barium titanate, strontium titanate, nickel titanate, and nickel-iron oxide with dissimilar metals.

[0207] (3) Resin composition)

[0208] The resin composition of this embodiment includes the modified block copolymer of component (I) and at least one component selected from the group consisting of components (II) to (IV).

[0209] Component (II): Free radical initiator.

[0210] Component (III): Polar resin (excluding component (I)).

[0211] Component (IV): Curing agent (excluding component (II)).

[0212] From the perspectives of lower dielectric constant, lower dielectric loss tangent, and / or flexibility of the resin composition and the cured product composed of the resin composition, it is preferable to use...

[0213] Component (I): the above-mentioned block copolymer,

[0214] Component (II): A resin composition consisting of a free radical initiator and a cured product of the resin composition.

[0215] As free radical initiators, any known substances can be used without particular limitation. Examples of thermal free radical initiators include hydrogen peroxides such as diisopropylbenzene hydroperoxide (Percumyl P), cumene hydroperoxide (Percumyl H), and tert-butyl hydroperoxide (Perbutyl H); dialkyl peroxides such as α,α-bis(tert-butylperoxy-m-isopropyl)benzene (Perbutyl P), dicumyl peroxide (Percumyl D), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (PERHEXA25B), tert-butylcumyl peroxide (Perbutyl C), di-tert-butyl peroxide (Perbutyl D), 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne (Perhexyne 25B), and tert-butylperoxy-2-ethylhexanoate (Perbutyl O); peroxide ketones; and n-butyl 4,4-di-(tert-butylperoxy)valerate (PERHEXA). V) such as peroxide ketals; peroxide diacyl groups; peroxide dicarbonates; organic peroxides such as peroxide esters; azo compounds such as 2,2-azobisisobutyl nitrile, 1,1'-(cyclohexane-1-1-carboxynitrile), 2,2'-azobis(2-cyclopropylpropionitrile), and 2,2'-azobis(2,4-dimethylpentanonitrile). These substances can be used alone or in combination.

[0216] In the resin composition of this embodiment, for the purpose of imparting properties such as heat resistance and adhesion to the substrate within the range of not impairing the dielectric properties of the cured product, it may contain component (III) polar resin (excluding component (I)), which tends to have excellent heat resistance by having polar groups.

[0217] When component (III) is a resin with free radical reactivity, the free radical initiation dose of component (II) can be adjusted arbitrarily according to the reactivity, or the component can be omitted.

[0218] The resin having free radical reactivity is not particularly limited; examples include homopolymers and / or copolymers with any compound containing at least one vinyl and / or halogen element in the polymer. From the perspective of dielectric properties, the presence of vinyl groups is preferred. Regarding the presence of vinyl groups, it can be a polymer composed of repeating units having vinyl groups, or a polymer having vinyl groups obtained by reacting a compound having vinyl and polar groups with the polar groups of a resin having polar groups. There are no particular limitations on compounds having polar groups and vinyl groups. Examples include (meth)acrylic acid (in this embodiment, "(meth)acrylic acid" refers to methacrylic acid or acrylic acid), maleic acid, monoalkyl maleate, fumaric acid, and other carboxyl-containing vinyl monomers; vinyl sulfonic acid, (meth)allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid, and other sulfonyl-containing vinyl monomers; hydroxystyrene, N-hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and other hydroxyl-containing vinyl monomers; 2-hydroxyethyl (meth)acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethylphosphonic acid, and other phosphate-containing vinyl monomers; and hydroxybenzene. Vinyl monomers containing hydroxyl groups, such as ethylene, N-hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol (meth)acrylate, and 1-buten-3-ol; vinyl monomers containing amino groups, such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate; vinyl monomers containing amide groups, such as (meth)acrylamide, N-methyl (meth)acrylamide, and N-butylacrylamide; vinyl monomers containing nitrile groups, such as (meth)acrylonitrile, cyanostyrene, and cyanoacrylate; glycidyl methacrylate, tetrahydrofurfuryl (meth)acrylate, and p-vinylphenylphenyl oxide; and vinyl monomers containing epoxy groups.

[0219] There are no particular limitations on monomers containing halogen elements; examples include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, and chloroprene.

[0220] If component (III) has low or no free radical reactivity, then from a reactivity perspective, a curing agent containing component (IV) is preferred. The curing agent (IV) typically functions to react with the polar resin of component (III) to cure the resin composition. "Reaction" between component (III) and component (IV) means that the polar groups of each component are covalently bonded to each other. When polar groups react with each other, for example, if the OH group of a carboxyl group is removed, the original polar group changes or disappears, thereby forming a covalent bond; this is included in the definition of "reactivity" of polar groups.

[0221] From the perspective of curing function, component (IV) curing agent preferably has at least two polar groups in one molecular chain that can react with the functional groups of component (III) polar resin. These groups can be used alone or in combination. There is no particular limitation on the types of polar groups possessed by components (III) and (IV); examples include:

[0222] Epoxy groups are associated with carboxyl, carbonyl, ester, imidazole, hydroxyl, amino, thiol, benzoxazine, carbodiimide, and phenolic hydroxyl groups.

[0223] Amino groups, carboxyl groups, carbonyl groups, hydroxyl groups, acid anhydride groups, sulfonic acid groups, and aldehyde groups;

[0224] Isocyanate groups are associated with hydroxyl groups, carboxylic acids, and phenolic hydroxyl groups;

[0225] Anhydride group and hydroxyl group;

[0226] Silanol group and hydroxyl, carboxylic acid group;

[0227] Halogens react with carboxylic acid groups, carboxylic acid ester groups, amino groups, phenolic groups, and mercapto groups;

[0228] Alkoxy groups, hydroxyl groups, alkoxide groups, and amino groups;

[0229] Maleimide and cyanate groups; etc.

[0230] Whether the bonding of these polar groups is component (III) or component (IV) can be arbitrarily chosen.

[0231] In addition, the case where the polar groups of component (III) and the polar groups of component (IV) do not react directly, but can react by adding a curing accelerator such as a catalyst, is also included in the definition of "reactivity".

[0232] For example, in the case where component (III) is a resin with epoxy groups and component (IV) is a curing agent with an anhydride group, the epoxy groups typically have very low reactivity with the anhydride group. However, by adding an amino compound as a curing accelerator, the epoxy groups of component (III) react with the amino groups, and some or all of the epoxy groups in component (III) become hydroxyl groups. By reacting these hydroxyl groups with the anhydride groups of the curing agent in component (IV), the resin composition is cured.

[0233] From a reactivity perspective, the ratio of polar resin (III) to curing agent (IV) in terms of the molar ratio of polar groups is preferably 1:0.01 to 1:20, more preferably 1:0.05 to 1:15, and even more preferably 1:0.1 to 1:10.

[0234] There are no particular limitations on the curing agent. For example, examples of curing agents with ester groups include EXB9451, EXB9460, EXB, 9460S, HPC8000-65T, HPC8000H-65TM, EXB8000L-65TM, EXB8150-65T, and EXB9416-70BK manufactured by DIC Corporation, and YLH1026, DC808, YLH1026, YLH1030, and YLH1048 manufactured by Mitsubishi Chemical Corporation.

[0235] There are no particular limitations on curing agents containing hydroxyl groups. Examples include MEH-7700, MEH-7810, MEH-7851, NHN, CBN, and GPH manufactured by Nippon Kayaku Co., Ltd., SN170, SN170, SN180, SN190, SN475, SN485, SN495, SN-495V, and SN375 manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd., and TD-2090, LA-7052, LA-7054, LA-1356, LA-3018-50P, and EXB-9500 manufactured by DIC Corporation.

[0236] There are no particular limitations on curing agents containing benzoxazine groups; examples include ODA-BOZ manufactured by JFE Chemical Co., Ltd., HFB2006M manufactured by Showa Polymer Co., Ltd., and Pd and Fa manufactured by Shikoku Chemical Co., Ltd.

[0237] There are no particular limitations on curing agents containing isocyanate groups. Examples include bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethidediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethide))benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether, etc., which are difunctional cyanate resins; polyfunctional cyanate resins derived from phenolic varnishes and cresol varnishes, etc.; prepolymers obtained by partially triazinizing these cyanate resins; and so on. As commercially available products, examples include PT30, PT60, ULL-950S, BA230, and BA230S75 manufactured by Lonza Japan.

[0238] There are no particular limitations on curing agents containing carbodiimide groups; for example, V-03 and V-07 manufactured by Nisshinbo Chemical Co., Ltd. can be cited.

[0239] There are no particular limitations on the type of curing agent containing amino groups, and examples include 4,4'-methylenebis(2,6-dimethylaniline), diphenyl diamino sulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3- Amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Commercially available products include KAYABOND C-200S, KAYABOND C-100, KAYAHARD AA, KAYAHARD AB, KAYAHARD AS manufactured by Nippon Kayaku Co., Ltd., and Epicure W manufactured by Mitsubishi Chemical Co., Ltd.

[0240] Furthermore, from a reactivity perspective, primary amines and / or secondary amines are preferred as amino groups, with primary amines being more preferred.

[0241] There are no particular limitations on curing agents containing anhydride groups; examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl norbornene, hydrogenated methyl norbornene, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and trimellitic acid. Polymer anhydrides such as pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic anhydride, 3,3'-4,4'-diphenyl sulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthol [1,2-C]furan-1,3-dione, ethylene glycol bis(triphenylamine), and styrene-maleic acid resin copolymerized from styrene and maleic acid.

[0242] Furthermore, the compounds having at least two structures with free radical reactivity also have the function of reacting with component (III) to cure the resin composition. There are no particular limitations on compounds having at least two structures with free radical reactivity; examples include allyl monomers such as triallyl isocyanurate (TAIC manufactured by Mitsubishi Chemical Corporation), tris(2-hydroxyethyl) isocyanurate, diallyl fumarate, diallyl adipate, triallyl citrate, and diallyl hexahydrophthalate.

[0243] As component (III) polar resin, from the aspects of heat resistance and adhesion mentioned above, it is preferably selected from at least one of the group consisting of epoxy resin, polyimide resin, polyphenylene ether resin, liquid crystal polyester resin and fluorine resin, more preferably selected from at least one of the group consisting of epoxy resin, polyimide resin and polyphenylene ether resin, and even more preferably epoxy resin.

[0244] From the perspective of heat resistance, any polyimide resin that has an imide bond in the repeating unit and falls within the category of polyimide resins is acceptable, without particular limitation. Examples include the structure of a common polyimide obtained by polycondensation (imide bonding) of a tetracarboxylic acid or its dianhydride with a diamine. From the perspective of curability, it is preferable to have unsaturated groups at the ends of the aforementioned polyimide structure. There are no particular limitations on polyimide resins with unsaturated groups at the ends; examples include maleimide-type polyimide resins, nadicimide-type polyimide resins, and allyl nadicimide-type polyimide resins. There are no particular restrictions on the tetracarboxylic acid or its dianhydride; for example, aromatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aliphatic tetracarboxylic acid dianhydrides can be used, either alone or in combination of two or more. There are no particular restrictions on the diamine; for example, aromatic diamines, alicyclic diamines, and aliphatic diamines commonly used in the synthesis of polyimides can be used. They can be used individually or in combination of two or more. In addition, from the perspective of reducing dielectric constant and reducing dielectric loss tangent, it is preferable that at least one of the above-mentioned tetracarboxylic acid or its dianhydride or diamine has one or more functional groups selected from the group consisting of fluorine group, trifluoromethyl group, hydroxyl group, sulfone group, carbonyl group, heterocyclic group, long-chain alkyl group, allyl group, etc.

[0245] Alternatively, commercially available polyimide resins can be used, including, but not limited to, Neoprim (registered trademark) C-3650 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neoprim C-3G30 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neoprim C-3450 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), Neoprim P500 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name), BT (bismaleimide triazine) resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.), JL-20 (manufactured by Shin Nippon Rika Co., Ltd., trade name) (the varnishes of these polyimide resins may contain silica), RIKACOAT SN20 manufactured by Shin Nippon Rika Co., Ltd., and RIKACOAT PN20, Pyre-ML manufactured by IST Corporation, Upia-AT, Upia-ST, Upia-NF, Upia-LB manufactured by Ube Industries, PIX-1400, PIX-3400, PI2525, PI2610, HD-3000, AS-2600 manufactured by Hitachi Chemical, HPC-5000, HPC-5012, HPC-1000, HPC-5020, HPC-3010, HPC-6000, HPC-9000, HCI-7000, HCI-1000S, HCI-1200E, HCI-1300 manufactured by Showa Denko Corporation, BMI-2300 manufactured by Daiwa Chemical Industries, Ltd., and MIR-3000 manufactured by Shin Nippon Chemical Co., Ltd.

[0246] As a polyphenylene ether resin, any substance falling under the category of polyphenylene ether resin can be used, containing phenylene ether units as repeating structural units. Alternatively, it may contain other structural units besides phenylene ether units.

[0247] As a homopolymer containing phenylene ether units, there are no particular restrictions on whether the phenylene in the phenylene unit has substituents. Examples of substituents include acryloyl groups such as ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl, as well as cyclohexyl groups such as vinyl, allyl, isopropenyl, 1-butenyl, 1-pentenyl, p-vinylphenyl, p-isopropenylphenyl, m-vinylphenyl, m-isopropenylphenyl, o-vinylphenyl, o-isopropenylphenyl, p-vinylbenzyl, p-isopropenylbenzyl, m-vinylbenzyl, m-isopropenylbenzyl, o-vinylbenzyl, o-isopropenylbenzyl, p-vinylphenylvinyl, p-vinylphenylpropenyl, p-vinylphenylbutenyl, m-vinylphenylvinyl, m-vinylphenylpropenyl, m-vinylphenylbutenyl, o-vinylphenylvinyl, o-vinylphenylvinyl, p-vinylphenylpropenyl, p-vinylphenylbutenyl, m-vinylphenylvinyl, m-vinylphenylpropenyl, m-vinylphenylbutenyl, o-vinylphenylvinyl, o-vinylphenyl Substituents containing unsaturated bonds, such as methyl phenylpropenyl, o-vinylphenylbutenyl, methacryloyl, acryloyl, 2-ethylacryloyl, 2-hydroxymethacryloyl, hydroxyl, carboxyl, carbonyl, thiocarbonyl, acyl halide, acid anhydride, carboxylic acid, thiocarboxylic acid, aldehyde, thioaldehyde, carboxylic acid ester, amide, sulfonic acid, sulfonate, phosphate, phosphate ester, amino, imino, nitrile, pyridinyl, quinolinyl, epoxy, thioepoxy, thioether, isocyanate, isothiocyanate, silicon halide, silanol, alkoxysilyl, tin halide, boric acid, boron-containing, borate, alkoxytin, and phenyltin, are preferably substituents containing any polar groups, in order to have free radical reactivity and / or reactivity with component (IV) curing agent.

[0248] From the perspective of the curability of the resin composition of this embodiment, the molecular weight of the polyphenylene ether resin is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less. Furthermore, the polyphenylene ether resin can be linear, cross-linked, or branched.

[0249] As a liquid crystal polyester resin, any polyester that forms an anisotropic molten phase can be classified as a liquid crystal polyester resin. Examples include Eastman Kodak's "X7G", Dartco's Xyday, Sumitomo Chemical's EKONOL, and Ceranese's Vectra.

[0250] As a fluorinated resin, any substance belonging to the category of fluorinated resins is acceptable; it is an olefin polymer containing fluorine groups. There are no particular limitations on what constitutes a fluorinated resin; examples include polytetrafluoroethylene, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, perfluoroethylene-propylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, and ethylene-chlorotrifluoroethylene copolymer.

[0251] As an epoxy resin, any substance falling under the category of epoxy resin is acceptable. From a strength perspective, it is preferable to have two or more epoxy groups per molecule. Epoxy resins can be used alone or in combination of two or more. There are no particular limitations on epoxy resins. Examples include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenol-type epoxy resins, naphthol phenolic varnish-type epoxy resins, phenol phenolic varnish-type epoxy resins, tert-butylcatechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol phenolic varnish-type epoxy resins, biphenyl-type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, epoxy resins containing spirocyclic rings, cyclohexane-type epoxy resins, cyclohexanediol-type epoxy resins, naphthylene ether-type epoxy resins, tris(hydroxymethyl)-type epoxy resins, and tetraphenylethane-type epoxy resins.

[0252] Furthermore, from a reactivity perspective, when using an epoxy resin as component (III), it is preferable to include a curing agent as component (IV). The polar groups of the curing agent as component (IV) are not particularly limited, and examples include carboxyl, imidazole, hydroxyl, amino, thiol, benzoxazine, and carbodiimide. From a reactivity perspective, carboxyl, imidazole, hydroxyl, benzoxazine, and carbodiimide are preferred, and from a dielectric property perspective, hydroxyl, carboxyl, imidazole, benzoxazine, and carbodiimide are more preferred, and hydroxyl, carboxyl, and carbodiimide are even more preferred.

[0253] Furthermore, when using two or more polar resins with different free radical reactivity as component (III), from the perspective of curability, the free radical initiator of component (II) and component (IV) can be used together. For example, when using maleimide-type polyimide resin with excellent free radical reactivity and bisphenol A epoxy resin without free radical reactivity as component (III), from the perspective of curability, the aforementioned free radical initiator of component (II) and the aforementioned curing agent of component (IV) can be added.

[0254] Furthermore, when a high-melting-point and high-rigidity polar resin is used as component (III), component (IV) may be omitted. There are no particular limitations on the high-melting-point and high-rigidity resin; examples include liquid crystal polyester resins and fluorinated resins such as polytetrafluoroethylene. By making component (III) high-melting-point and high-rigidity, the required heat resistance and / or strength can be achieved even without component (IV).

[0255] The resin composition of this embodiment may further include a curing accelerator, filler, flame retardant, and other additives as component (V). Furthermore, the additives included as component (I) of the modified block copolymer also have the same meaning as components (V) of the resin composition described above.

[0256] Curing accelerators are added to promote the reactivity between the above-mentioned components and can be any known substances. Examples include, but are not limited to, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. A single curing accelerator can be used, or two or more can be used in combination.

[0257] There are no particular limitations on phosphorus-based curing accelerators. Examples include triphenylphosphine, phosphorium borate compounds, tetraphenylphosphine tetraphenyl borate, n-butylphosphine tetraphenyl borate, tetrabutylphosphine decanoate, (4-methylphenyl)triphenylphosphine thiocyanate, tetraphenylphosphine thiocyanate, and butyltriphenylphosphine thiocyanate. Triphenylphosphine and tetrabutylphosphine decanoate are preferred.

[0258] There are no particular limitations on the amine-based curing accelerators. Examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyl dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0259] There are no particular limitations on imidazole-based curing accelerators; examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole ontium trimellitate, 1-cyanoethyl-2-phenylimidazole ontium trimellitate, 2,4-diamino-6-[2'-methylimidazole-(1')]-ethyl-triazine, 2,4- Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzyl chloride imidazolyl, 2-methylimidazoline, 2-phenylimidazoline and other imidazolium compounds, as well as adducts of imidazolium compounds with epoxy resins, preferably 2-ethyl-4-methylimidazolium and 1-benzyl-2-phenylimidazolium.

[0260] As an imidazole-based curing accelerator, commercially available products can be used, such as, but not limited to, P200-H50 manufactured by Mitsubishi Chemical Corporation.

[0261] There are no particular limitations on the guanidine-based curing accelerators, and examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc., with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

[0262] There are no particular limitations on what constitutes a metal-based curing accelerator; examples include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) and cobalt(III) acetylacetone, organocopper complexes such as copper(II) acetylacetone, organozinc complexes such as zinc(II) acetylacetone, organoiron complexes such as iron(III) acetylacetone, organonickel complexes such as nickel(II) acetylacetone, and organomanganese complexes such as manganese(II) acetylacetone. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0263] 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.

[0264] These fillers can be used alone or in combination.

[0265] The shape of these fillers can be any shape, such as flakes, spheres, granules, powders, or amorphous shapes, without any particular limitation.

[0266] Resin compositions or cured products are often exposed to high temperatures during molding and other processes. To prevent shrinkage and deformation of the molded body due to temperature changes, a low coefficient of linear expansion is preferred. From the perspective of reducing the coefficient of linear expansion, silica is preferred as a filler. There are no particular limitations on silica, and examples include amorphous silica, molten silica, crystalline silica, synthetic silica, and hollow silica.

[0267] There are no particular limitations on flame retardants. Examples include 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 such as hexabromobenzene, decabromodiphenyl ethane, 4,4-dibromobiphenyl, and ethylenebis(tetrabromophthalimide). These flame retardants can be used alone or in combination of two or more. The aforementioned flame retardants also include so-called flame retardant additives, which have low inherent flame retardant properties but can achieve a synergistic effect when used in combination with other flame retardants.

[0268] Fillers and flame retardants can also be of the type that have undergone pre-surface treatment using surface treatment agents such as silane coupling agents. There are no particular limitations on the surface treatment agent; examples include fluorinated silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. They can be used alone or in combination.

[0269] As other additives, there are no particular limitations on substances that are commonly used in the formulation of resin compositions and / or cured products. Examples of such 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.

[0270] Based on the aforementioned aspects of low dielectric constant and low dielectric loss tangent, it is preferable to avoid the presence of pigments, colorants, lubricants, anti-sticking agents, and antistatic agents.

[0271] The resin composition in this embodiment can be formed by melt-blending the components or by dissolving them in a solvent capable of dissolving the components and stirring (hereinafter referred to as "varnish"). From a processability perspective, varnish is preferred. There are no particular limitations on the solvent; examples include 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. One organic solvent can be used alone, or two or more can be used in combination.

[0272] (cured material)

[0273] The cured product of this embodiment comprises the modified block copolymer described above. Furthermore, the cured product of this embodiment is preferably a cured product of the above-described resin composition.

[0274] In this specification, "cured product" refers to a substance obtained by subjecting the above-described resin composition to a curing reaction at any temperature and time. It is a concept encompassing not only the overall cured state of the composition but also the cured state of at least a portion of the resin components (semi-cured). Therefore, in the case of a cured product in a semi-cured state, a step of heating the cured product to cure the uncured components can be included. Specifically, as conditions for the curing step, the reaction temperature 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 is a varnish, the curing reaction is preferably carried out after the solvent has been removed. As a drying method, it can be carried out by existing known methods such as heating or blowing hot air, preferably at a temperature lower than the curing reaction temperature, and the drying is performed such that the solvent content in the resin composition is 10% by mass or less, preferably 5% by mass or less.

[0275] (Adhesive)

[0276] The adhesive in this embodiment comprises the modified block copolymer described above. Alternatively, the adhesive in this embodiment preferably comprises the resin composition described above.

[0277] (Resin film)

[0278] The resin film of this embodiment comprises the above-described resin composition.

[0279] The resin film used in this embodiment is not particularly limited. For example, the varnish described above can be spread on a uniform film, dried as described above to remove the solvent, and then rolled into a roll for storage. If the resin sheet has a protective film, it can be used by peeling off the protective film.

[0280] (prepreg)

[0281] The prepreg in this embodiment is a composite of the substrate and the above-described resin composition.

[0282] The prepreg in this embodiment preferably comprises a substrate and the aforementioned resin composition impregnated or coated onto the substrate. The prepreg can be obtained by, but is not particularly limited to, impregnating the substrate, such as with the aforementioned varnish, with a glass cloth and then removing the solvent using the aforementioned drying method. The substrate is not particularly limited; examples include various types of glass cloth 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, and felt; natural cellulose-based substrates such as carbon fiber cloth, kraft paper, cotton paper, and cloth made from paper-glass blended filaments; and polytetrafluoroethylene porous membranes. From the perspective of dielectric properties, glass cloth is preferred. These substrates can be used individually or in combination of two or more.

[0283] In the prepreg of this embodiment, the proportion of the solid component of the above-mentioned resin composition is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. When the above proportion is 30% by mass or more, the prepreg tends to have superior insulation reliability when used for applications such as electronic substrates. When the above proportion is 80% by mass or less, the prepreg tends to have superior mechanical properties such as rigidity in applications such as electronic substrates.

[0284] (laminated body)

[0285] The laminate in this embodiment is a laminate formed by laminating the cured prepreg and / or the cured resin composition with a metal foil and / or a thermosetting resin. Preferably, the metal foil is copper foil and the thermosetting resin is a polyimide-based resin. Alternatively, the laminate in this embodiment is preferably a laminate formed by laminating the cured prepreg or the cured resin composition with a metal foil.

[0286] The laminate of this embodiment can be manufactured using, but is not particularly limited to, cured products of, for example, block copolymers. Such a laminate can be manufactured through, but is not particularly limited to, processes such as those described below:

[0287] Step (a): A process of forming a resin layer by depositing a resin film containing the above-mentioned block copolymer on a substrate;

[0288] Process (b): A process of planarizing the resin layer by heating and pressurizing;

[0289] Process (c): The process of further forming a wiring layer on the resin layer; etc.

[0290] In step (a), the method for depositing the resin layer on the substrate is not particularly limited. Examples include using a multi-stage press, a vacuum press, a normal pressure laminator, or a laminator that applies heat and pressure under vacuum. A laminator that applies heat and pressure under vacuum is preferred. In this method, even if the circuit substrate has fine wiring circuits on its surface, the spaces between the circuits can be filled with resin without gaps. Furthermore, lamination can be done in batches or continuously using rollers or the like.

[0291] There are no particular limitations on the substrate; for example, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, polyphenylene ether substrates, fluoropolymer substrates, etc., can be used. The surfaces of the laminated resin layers on the substrate can be roughened beforehand, and there is no limitation on the number of substrate layers.

[0292] In step (b), the resin film laminated in step (a) and the substrate are planarized under heat and pressure. The conditions can be adjusted arbitrarily according to the type of substrate and the composition of the resin film, for example, the preferred range is temperature 100-300°C, pressure 0.2-20 MPa, and time 30-180 minutes.

[0293] In step (c), a circuit layer is further formed on the resin layer produced by pressing the resin film and the substrate under heat. There is no particular limitation on the formation method, and existing known methods can be cited, such as etching methods such as subtractive etching, semi-additive etching, etc.

[0294] The subtractive process involves forming a resist layer on a metal layer with a shape corresponding to the desired pattern. The portion of the metal layer that was removed by the resist is then dissolved and removed by a reagent during the subsequent development process, thereby forming the desired circuit.

[0295] The semi-addition method is as follows: a metal coating is formed on the surface of a 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, and then a metal layer is formed by an electrolytic plating method. The unwanted electroless plating layer is removed using reagents, etc., to form the desired circuit layer.

[0296] In addition, 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. For example, NC drill bits, carbon dioxide lasers, UV lasers, YAG lasers, plasma, etc., can be used.

[0297] Furthermore, the laminate in this embodiment can be a flexible material or a laminated plate. The laminated plate can be a metal-clad laminate. The metal-clad laminate is obtained, for example, by laminating the above-mentioned resin composition or the above-mentioned prepreg with a metal foil and then curing it, and removing a portion of the metal foil from the metal-clad laminate. The metal-clad laminate preferably has a form in which a cured prepreg (also called a "cured composite") and a metal foil are laminated and bonded together, making it suitable for use as a material for electronic circuit board substrates. There are no particular limitations on the metal foil; for example, aluminum foil and copper foil can be used, among which copper foil has low resistance and is therefore preferred. The cured composite combined with the metal foil can be a single sheet or multiple sheets, and the metal foil is overlapped on one or both sides of the composite and processed into a laminate, depending on the application. There is no particular limitation on the manufacturing method of the laminate. For example, the following method can be used: forming a composite material (e.g., the prepreg described above) consisting of a thermosetting resin composition and a substrate, overlapping it with a metal foil, and then curing the thermosetting resin composition to obtain a laminate formed by laminating the cured laminate with the metal foil. One particularly preferred application of the above-mentioned laminate is a printed wiring board. In the printed wiring board, it is preferable to remove at least a portion of the metal foil from the metal-clad laminate. The printed wiring board of this embodiment can be typically formed by using the above-mentioned prepreg for pressure heating molding. As the substrate, the same substrate as the one mentioned above in the prepreg can be cited. The printed wiring board of this embodiment has excellent strength and electrical properties (low dielectric constant and low dielectric loss tangent) by containing the above-mentioned resin composition, thereby suppressing the variation of electrical properties associated with environmental changes, and thus having excellent insulation reliability and mechanical properties.

[0298] (Electronic circuit board materials)

[0299] The electronic circuit board material of this embodiment includes a cured product containing the modified block copolymer described above, or a cured product containing the resin composition described above.

[0300] The electronic circuit board material of this embodiment is formed using, but is not particularly limited to, the resin composition and / or varnish described above. Specifically, but not particularly limited, the electronic circuit board material of this embodiment is, for example, a cured product formed by curing the resin composition described above, a resin film containing the cured product of the resin composition described above, an impregnation composite of a substrate and a resin (also referred to as "prepreg" in this disclosure), or a metal foil containing resin, or a printed wiring board containing at least one of these.

[0301] Example

[0302] The following specific embodiments and comparative examples illustrate this implementation method in detail, but this implementation method is not limited to any of the following embodiments and comparative examples.

[0303] It should be noted that the structure identification and property determination of the block copolymers (component (I)) used in the following examples and comparative examples were carried out as follows.

[0304] [Methods for identifying the structure and determining the physical properties of polymers]

[0305] ((1) Content of vinyl aromatic compounds in block copolymers)

[0306] The measurements were performed using a UV spectrophotometer (Shimadzu Corporation, UV-2450) on the unhydrogenated block copolymer.

[0307] (2) Vinyl bond content of block copolymers)

[0308] The unhydrogenated block copolymers were used, and measurements were performed using an infrared spectrophotometer (FT / IR-230, manufactured by Nippon Spectrophotometer Co., Ltd.). The vinyl bond content of the block copolymers was calculated using the Hampton method.

[0309] (3) Molecular weight and molecular weight distribution of block copolymers)

[0310] The molecular weight of the block copolymer before modification and hydrogenation was determined by GPC [Apparatus: LC-10 (Shimadzu Corporation), Column: TSK gel GMHXL (4.6mm×30cm)].

[0311] Tetrahydrofuran was used as the solvent. The determination was performed at 35°C. The weight-average molecular weight was calculated using a calibration curve derived from the determination of commercially available standard polystyrene (using the peak molecular weight of standard polystyrene).

[0312] It should be noted that, regarding the molecular weight in the case of multiple peaks in a chromatogram, it is assumed to be the average molecular weight calculated based on the molecular weight of each peak and the composition ratio of each peak (obtained from the area ratio of each peak in the chromatogram). Furthermore, the molecular weight distribution is the ratio of the obtained weight-average molecular weight (Mw) to the number-average molecular weight (Mn) (Mw / Mn).

[0313] (4) Hydrogenation rate of double bonds in the conjugated diene monomer units of the block copolymer)

[0314] The hydrogenation rate of the double bonds in the conjugated diene monomer units was determined using a nuclear magnetic resonance (NMR) apparatus (BRUKER DPX-400).

[0315] (4-1) Total hydrogenation rate, vinyl hydrogenation rate

[0316] The total hydrogenation rate is the sum of the content of hydrogenated alkenyl monomer units (a1) of unit (a) as described above, and the content of hydrogenated alkenyl monomer units (b1) of 1,4-bonded unit (b) as conjugated diene compounds, when the total content of polymer block (B) is set to 100%. The hydrogenation rate (%) of the hydrogenated block copolymer was determined using a nuclear magnetic resonance apparatus (a "DPX-400" manufactured by BRUKER).

[0317] In addition, the vinyl hydrogenation rate (%) is calculated as the ratio of the above unit (a1) to the above unit (a) when the amount of the 1,2-bonded and / or 3,4-bonded unit (a) in the polymer block (B) is set to 100% (vinyl hydrogenation rate: (a1) / (a)).

[0318] (5) Metal content

[0319] The metal content (i.e., the total content of Ti, Ni, Li and Co) in the block copolymer was determined by elemental analysis using inductively coupled plasma (ICP, "ICPS-7510" manufactured by Shimadzu Corporation).

[0320] (6) The bonding position of the "polar group"

[0321] The binding sites of the "polar groups" in the modified block copolymers were confirmed by analyzing the modified block copolymers using a nuclear magnetic resonance (NMR) device.

[0322] ((7) Amount of amino addition in hydrogenated terminal amino-modified block copolymers)

[0323] In modified block copolymers, when the terminal amino group is a polar group, the amount of addition is determined as follows.

[0324] By utilizing the adsorption properties of modified components on a GPC column packed with silica gel, for a sample solution containing hydrogenated terminal amino-modified block copolymer and low molecular weight internal standard polystyrene (PS), the ratio of hydrogenated terminal amino-modified block copolymer to standard polystyrene in the chromatogram determined in (3) above is compared with the ratio of hydrogenated terminal amino-modified block copolymer to standard polystyrene in the chromatogram determined using a silica-based GPC column [Apparatus: LC-10 (Shimadzu Corporation), Column: Zorbax (DuPont)]. The adsorption amount on the silica column is determined by the difference between them, and the ratio is taken as the modification rate. Regarding the amount of terminal amino addition, the amount of addition (mass%) is calculated based on the proportion (%) of amino groups calculated by the following formula and the molecular weight of the block copolymer.

[0325] [Number 1]

[0326]

[0327] a: Area (%) of all polymers determined using polystyrene-based gel (PLgel)

[0328] b: Area (%) of low molecular weight internal standard PS determined using polystyrene gel (PLgel)

[0329] c: Area (%) of all polymers determined using a silica-based column (Zorbax).

[0330] d: Area (%) of low molecular weight internal standard PS determined using a silica-based column (Zorbax)

[0331] [Preparation of hydrogenation catalysts]

[0332] In the examples and comparative examples described later, the hydrogenation catalyst used in the production of hydrogenated block copolymers was prepared by the following method.

[0333] The reaction vessel equipped with a stirring device was purged with nitrogen, and 1 liter of dry, purified cyclohexane was added into it.

[0334] Next, 100 mmol of bis(n-5-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 approximately 3 days. This yielded the hydrogenation catalyst.

[0335] <Component (I) Block copolymer>

[0336] Block copolymers of vinyl aromatic compounds and conjugated dienes are prepared as follows.

[0337] The structural values ​​and residual metal content of each block copolymer are shown in Tables 1-4.

[0338] (Hydrogenated block copolymer(1))

[0339] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0340] First, add a cyclohexane solution containing 45 parts by mass of styrene (concentration 20% by mass).

[0341] Next, 0.10 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 30 minutes.

[0342] Next, a cyclohexane solution containing 55 parts by mass of butadiene (20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0343] Next, a hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 50 ppm relative to Ti per 100 parts by mass of the block copolymer, and the hydrogenation reaction was carried out for about 2 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C.

[0344] The resulting hydrogenated block copolymer (1) solution was further subjected to a deashing operation as shown below, thereby reducing the metal content caused by the initiator and hydrogenation catalyst. Specifically, 30 parts by mass of a water / sulfuric acid mixture were added relative to 100 parts by mass of the hydrogenated block copolymer. It should be noted that the amount of sulfuric acid added was adjusted so that the pH of the water removed by the decanter in subsequent steps was 7.0. Most of the water in the solution was removed by the decanter until the amount of water was 3 parts by mass, and 0.4 mol of carbon dioxide was added relative to 1 mol of the initiator metal for mixing. Subsequently, 0.3 parts by mass of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was added as a stabilizer. The solution was treated using the stripping method described in Japanese Patent Publication No. 05-54845 (a method of removing most of the solvent in water at 90-98°C, and then feeding an aqueous dispersion slurry with a particle concentration of about 5% by weight into a twin-screw extruder to remove the solvent), thereby obtaining a hydrogenated block copolymer (1).

[0345] The hydrogenated block copolymer (1) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 8.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 35%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0346] (Hydrogenated block copolymer(2))

[0347] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0348] First, add a cyclohexane solution containing 22.5 parts by mass of styrene (concentration 20% by mass).

[0349] Next, 0.10 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[0350] Next, a cyclohexane solution containing 55 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[0351] Next, a cyclohexane solution containing 22.5 parts by mass of styrene (20% by mass) was added, and polymerization was carried out for 20 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0352] The obtained block copolymer was further hydrogenated and deashed under the same conditions as the block copolymer (1).

[0353] The hydrogenated block copolymer (2) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 8.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 36%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0354] (Hydrogenated block copolymer (3))

[0355] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0356] First, add a cyclohexane solution containing 5 parts by mass of butadiene (concentration 20% by mass).

[0357] Next, 0.10 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 5 minutes.

[0358] Next, a cyclohexane solution containing 45 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 30 minutes.

[0359] Next, a cyclohexane solution containing 50 parts by mass of butadiene (20% by mass) was added, and polymerization was carried out for 30 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0360] The obtained block copolymer was further hydrogenated and deashed under the same conditions as the block copolymer (1).

[0361] The hydrogenated block copolymer (3) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 8.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 36%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0362] (Hydrogenated block copolymer (4))

[0363] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0364] First, add a cyclohexane solution containing 12.5 parts by mass of butadiene (concentration 20% by mass).

[0365] Next, 0.10 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 15 minutes.

[0366] Next, a cyclohexane solution containing 75 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 40 minutes.

[0367] Next, a cyclohexane solution containing 12.5 parts by mass of butadiene (20% by mass) was added, and polymerization was carried out for 15 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0368] The obtained block copolymer was further hydrogenated and deashed under the same conditions as the block copolymer (1).

[0369] The hydrogenated block copolymer (4) obtained above has a styrene content of 75% by mass and a weight-average molecular weight of 8.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 36%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 95%.

[0370] (Hydrogenated block copolymer (5))

[0371] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0372] First, add a cyclohexane solution containing 5 parts by mass of butadiene (concentration 20% by mass).

[0373] Next, 0.071 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 1.3 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 5 minutes.

[0374] Next, a cyclohexane solution containing 30 parts by mass of styrene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[0375] Next, a cyclohexane solution containing 35 parts by mass of butadiene (concentration 20% by mass) is added, and polymerization is carried out for 15 minutes.

[0376] Next, a cyclohexane solution containing 30 parts by mass of styrene (20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0377] The obtained block copolymer was further hydrogenated and deashed under the same conditions as the block copolymer (1).

[0378] The hydrogenated block copolymer (5) obtained above has a styrene content of 60% by mass and a weight-average molecular weight of 11.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 74%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0379] (Hydrogenated block copolymer (6))

[0380] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0381] First, add a cyclohexane solution containing 32.5 parts by mass of styrene (concentration 20% by mass).

[0382] Next, 0.13 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 70°C for 30 minutes.

[0383] Next, a cyclohexane solution containing 35 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[0384] Next, a cyclohexane solution containing 32.5 parts by mass of styrene (20% by mass) was added, and polymerization was carried out for 30 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0385] The obtained block copolymer was further hydrogenated and deashed under the same conditions as the block copolymer (1).

[0386] The hydrogenated block copolymer (6) obtained above has a styrene content of 65% by mass and a weight-average molecular weight of 6.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units (a) from 1,2-bonded and / or 3,4-bonded (vinyl bond content: unit (a) / block (B)) is 41%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0387] (Hydrogenated block copolymer (7))

[0388] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0389] First, add a cyclohexane solution containing 22.5 parts by mass of styrene (concentration 20% by mass).

[0390] Next, 0.17 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 70°C for 40 minutes.

[0391] Next, a cyclohexane solution containing 55 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 10 minutes.

[0392] Next, a cyclohexane solution containing 22.5 parts by mass of styrene (20% by mass) was added, and polymerization was carried out for 40 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0393] The obtained block copolymer was further hydrogenated and deashed under the same conditions as the block copolymer (1).

[0394] The hydrogenated block copolymer (7) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 4.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 40%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 93%.

[0395] (Hydrogenated block copolymer (8))

[0396] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0397] First, add a cyclohexane solution containing 22.5 parts by mass of styrene (concentration 20% by mass).

[0398] Next, 0.10 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 1.3 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 55°C for 40 minutes.

[0399] Next, a cyclohexane solution containing 55 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 55°C for 20 minutes.

[0400] Next, a cyclohexane solution containing 22.5 parts by mass of styrene (20% by mass) was added, and polymerization was carried out for 40 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0401] The obtained block copolymer was further hydrogenated and deashed under the same conditions as the block copolymer (1).

[0402] The hydrogenated block copolymer (8) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 8.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 75%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0403] (Hydrogenated block copolymer (9))

[0404] Except that the same operation as that for the hydrogenated block copolymer (7) is performed, the n-butyllithium is made to be 0.080 parts by mass relative to 100 parts by mass of all monomers.

[0405] The hydrogenated block copolymer (9) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 11.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 35%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0406] (Hydrogenated block copolymer (10))

[0407] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0408] First, add a cyclohexane solution containing 25 parts by mass of styrene (concentration 20% by mass).

[0409] Next, 0.13 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.12 mol of tetramethylethylenediamine (TMEDA) relative to 1 mol of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[0410] Next, a cyclohexane solution containing 55 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[0411] Next, a cyclohexane solution containing 25 parts by mass of styrene (20% by mass) was added, and polymerization was carried out for 20 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0412] The reaction time of the obtained block copolymer was further extended to 1 hour, and the same hydrogenation reaction as that of the hydrogenated block copolymer (1) was carried out, and deashing was carried out under the same conditions as that of the hydrogenated block copolymer (1).

[0413] The hydrogenated block copolymer (10) obtained above has a styrene content of 50% by mass and a weight-average molecular weight of 6.5 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 20%, the total hydrogenation rate is 50%, and the vinyl hydrogenation rate is 91%.

[0414] (block copolymer (11))

[0415] Except for not performing the hydrogenation reaction, the same operation as the hydrogenated block copolymer (10) is performed.

[0416] The hydrogenated block copolymer (11) obtained above has a styrene content of 50% by mass and a weight-average molecular weight of 6.5 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-bonded and / or 3,4-bonded units (a) (vinyl bond content: unit (a) / block (B)) is 20%, the total hydrogenation rate is 0.0%, and the vinyl hydrogenation rate is 0.0%.

[0417] (Hydrogenated block copolymer (12))

[0418] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0419] First, add a cyclohexane solution containing 25 parts by mass of styrene (concentration 20% by mass).

[0420] Next, 0.080 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.30 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[0421] Next, a cyclohexane solution (concentration 20% by mass) containing 35 parts by mass of butadiene and 15 parts by mass of styrene was added, and polymerization was carried out at 70°C for 20 minutes.

[0422] Next, a cyclohexane solution containing 25 parts by mass of styrene (20% by mass) was added, and polymerization was carried out for 20 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0423] The reaction time of the obtained block copolymer was further extended to 1 hour, and the same hydrogenation reaction as that of the hydrogenated block copolymer (1) was carried out, and deashing was carried out under the same conditions as that of the hydrogenated block copolymer (1).

[0424] The hydrogenated block copolymer (12) obtained above has a styrene content of 65% by mass and a weight-average molecular weight of 11.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of units (a) from 1,2-bonded and / or 3,4-bonded (vinyl bond content: unit (a) / block (B)) is 41%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0425] (Hydrogenated block copolymer (13))

[0426] Except for setting the hydrogenation reaction temperature to 60°C and the hydrogenation reaction time to 3 hours, the same operation as for hydrogenated block copolymer (8) is performed.

[0427] The hydrogenated block copolymer (13) obtained as described above has a styrene content of 45% by mass and a weight-average molecular weight of 8.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 75%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 78%.

[0428] (Hydrogenated block copolymer (14))

[0429] Except for adding 80 ppm hydrogenation catalyst, making the hydrogenation reaction time 1 hour, and not performing deashing, the same operation as for hydrogenated block copolymer (6) was performed.

[0430] The hydrogenated block copolymer (14) obtained as described above has a styrene content of 65% by mass and a weight-average molecular weight of 6.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 41%, the total hydrogenation rate is 96%, and the vinyl hydrogenation rate is 84%.

[0431] (Hydrogenated block copolymer (15))

[0432] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0433] First, add a cyclohexane solution containing 30 parts by mass of styrene (concentration 20% by mass).

[0434] Next, 0.10 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 25 minutes.

[0435] Next, a cyclohexane solution containing 70 parts by mass of butadiene (20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0436] The obtained block copolymer was further subjected to hydrogenation and deashing under the same conditions as the hydrogenated block copolymer (1).

[0437] The hydrogenated block copolymer (15) obtained above has a styrene content of 30% by mass and a weight-average molecular weight of 8.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 35%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0438] (block copolymer (16))

[0439] Batch polymerization was carried out using a tank reactor (10L internal volume) equipped with a stirring device and a jacket.

[0440] First, add a cyclohexane solution containing 15 parts by mass of styrene (concentration 20% by mass).

[0441] Next, 0.10 parts by mass of n-butyllithium relative to 100 parts by mass of all monomers and 0.2 mol of tetramethylethylenediamine (TMEDA) relative to 1 mole of n-butyllithium were added, and polymerization was carried out at 70°C for 20 minutes.

[0442] Next, a cyclohexane solution containing 70 parts by mass of butadiene (concentration 20% by mass) was added, and polymerization was carried out at 70°C for 20 minutes.

[0443] Next, a cyclohexane solution containing 15 parts by mass of styrene (20% by mass) was added, and polymerization was carried out for 20 minutes. Methanol was then added to stop the polymerization reaction, yielding a block copolymer.

[0444] The obtained block copolymer was further hydrogenated and deashed under the same conditions as the block copolymer (1).

[0445] The hydrogenated block copolymer (16) obtained above has a styrene content of 30% by mass and a weight-average molecular weight of 8.0 × 10⁻⁶. 4The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 35%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0446] (block copolymer (17))

[0447] Except that the same operation as that for the hydrogenated block copolymer (2) is performed, the n-butyllithium is made up of 0.29 parts by weight relative to 100 parts by weight of all monomers.

[0448] The hydrogenated block copolymer (17) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 3.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 36%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 94%.

[0449] (block copolymer (18))

[0450] Except that the same operation as that for the hydrogenated block copolymer (2) is performed, except that the n-butyllithium is 0.072 parts by mass relative to 100 parts by mass of all monomers.

[0451] The hydrogenated block copolymer (18) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 12.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 36%, the total hydrogenation rate is 98%, and the vinyl hydrogenation rate is 95%.

[0452] (block copolymer (19))

[0453] Except for not performing deashing, the same operation as the hydrogenated block copolymer (2) is performed.

[0454] The hydrogenated block copolymer (19) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 8.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 36%, the total hydrogenation rate is 97%, and the vinyl hydrogenation rate is 95%.

[0455] (block copolymer (20))

[0456] Before adding methanol, add 1.1 moles of 1,3-dimethyl-2-imidazolinone relative to 1 mole of n-butyllithium, react at 70°C for 15 minutes, otherwise perform the same operation as block copolymer (1).

[0457] The hydrogenated terminal amino-modified block copolymer (20) obtained above has a styrene content of 45% by mass and a weight-average molecular weight of 8.1 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond weight: unit (a) / block (B)) is 36%, the total hydrogenation rate is 91%, the vinyl hydrogenation rate is 95%, and the amount of terminal amino addition is 0.12 by mass.

[0458] (block copolymer (21))

[0459] Perform the same operation as with block copolymer (20) to obtain hydrogenated terminal amino modified block copolymer.

[0460] The hydrogenated terminal amino modified block copolymer obtained above was mixed with maleic anhydride and fed into a twin-screw extruder with the temperature set at 150-200°C over the entire length of the extruder for compounding, thereby obtaining a terminal carboxyl modified block copolymer (21).

[0461] The hydrogenated terminal carboxyl modified block copolymer (21) obtained as described above has a styrene content of 45% by mass and a weight-average molecular weight of 8.0 × 10⁻⁶. 4 The molecular weight distribution is 1.10, the content of 1,2-linked and / or 3,4-linked units (a) (vinyl bond content: unit (a) / block (B)) is 35%, the total hydrogenation rate is 90%, and the vinyl hydrogenation rate is 95%.

[0462] The obtained terminal carboxyl modified block copolymer (21) was subjected to GPC determination under the above conditions ((7) the amount of amino addition in the hydrogenated terminal amino modified block copolymer), and it was confirmed that no amino adsorption occurred on the column.

[0463] This means that all the amino groups in the hydrogenated terminal amino modified block copolymer reacted with maleic anhydride, and the amount of carboxyl group added to the resulting terminal carboxyl modified block copolymer (21) was 0.12 by mass, similar to that of the amino group.

[0464] [Table 1]

[0465]

[0466] [Table 2]

[0467]

[0468] [Table 3]

[0469]

[0470] [Table 4]

[0471]

[0472] (Modified copolymer)

[0473] Modified hydrogenated block copolymers M-(1) to M-(19) of the above-mentioned hydrogenated block copolymers (1) to (19) were prepared as follows.

[0474] The compounding was performed using a twin-screw extruder with the temperature set at 150–200°C throughout the length of the extruder. The screw rotation speed was approximately 250 rpm, and the extrusion rate was 5 kg per hour. Hydrogenated block copolymers (1) to (19) were fed with maleic anhydride in proportions shown in Tables 5–8 through the narrow passage of the extruder, and an organic peroxide (peroxide 25B (manufactured by Nippon Oil Co., Ltd.)) was fed from the downstream feed port of the extruder in proportions shown in Tables 5–8. The extruded wire was granulated and dried at approximately 80°C for 3 hours to obtain modified hydrogenated block copolymers M-(1) to M-(19). The amount of addition of polar groups in the obtained modified hydrogenated block copolymers M-(1) to M-(19) is shown in Tables 5–8.

[0475] Regarding the addition amount of maleic anhydride (polar group), the maleic anhydride-modified hydrogenated block copolymer was dissolved in toluene and titrated with a methanol solution of sodium methoxide with a coefficient of 1 ± 0.05 to calculate the addition amount. The residual maleic anhydride amount was calculated as follows: The maleic anhydride-modified hydrogenated block copolymer was refluxed in acetone at a concentration of approximately 1.5% by mass at 60°C for 2 hours and then thoroughly dried. The same titration was performed using this sample, and the residual maleic anhydride amount was calculated based on the titration values ​​before and after reflux.

[0476] [Table 5]

[0477]

[0478] [Table 6]

[0479]

[0480] [Table 7]

[0481]

[0482] [Table 8]

[0483]

[0484] <Methods for Determining the Physical Properties of Solidified Materials>

[0485] ((1) Dielectric loss tangent and dielectric constant)

[0486] The dielectric loss tangent at 10 GHz was determined using the cavity resonator method. A network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resornator CP series) manufactured by Kanto Electronics Application Development Co., Ltd. were used as the measurement apparatus. For the test samples, test pieces with a width of 2.6 mm and a length of 80 mm were cut from the cured film described later, and the dielectric loss tangent and dielectric constant were measured.

[0487] (Evaluation methods for [Examples 1-33] and [Comparative Examples 1-20])

[0488] The difference between the dielectric loss tangent and dielectric constant of Comparative Example 1 (which does not contain block copolymers) and each component was evaluated.

[0489] Dielectric loss tangent ◎: 0.010 or higher

[0490] ○: Above 0.0050 and below 0.010

[0491] △: Above 0.0030 and below 0.0050

[0492] ×: Less than 0.0030 (including the same value and positive difference)

[0493] Dielectric constant ◎: 0.35 or higher

[0494] ○: Above 0.30, less than 0.35

[0495] △: Above 0.20 and below 0.30

[0496] ×: Less than 0.20 (including both the same value and positive difference).

[0497] (Evaluation methods for [Examples 34-43] and [Comparative Examples 21-33])

[0498] The evaluation was conducted by comparing Comparative Example 21 (which does not contain block copolymers) with the differences between each component (Comparative Example 21 - each component).

[0499] Dielectric loss tangent

[0500] ◎:0.0012 or more

[0501] ○: 0.0010 or higher and less than 0.0012

[0502] △: 0.0080 or higher and less than 0.0010

[0503] ×: Less than 0.0080 (including the same value and positive difference)

[0504] Dielectric constant

[0505] ◎:0.12 or more

[0506] ○: 0.10 or higher and less than 0.12

[0507] △: 0.08 or higher and less than 0.10

[0508] ×: Less than 0.08 (including the same value and positive difference)

[0509] (Evaluation methods for [Examples 44-51] and [Comparative Examples 34-43])

[0510] The evaluation was conducted by comparing the difference between Comparative Example 34 (which does not contain block copolymers) and each component (Comparative Example 34 - each component).

[0511] Dielectric loss tangent

[0512] ◎:0.0012 or more

[0513] ○: 0.0010 or higher and less than 0.0012

[0514] △: 0.0080 or higher and less than 0.0010

[0515] ×: Less than 0.0080 (including the same value and positive difference)

[0516] Dielectric constant

[0517] ◎:0.15 or more

[0518] ○: 0.12 or higher and less than 0.15

[0519] △: 0.10 or higher and less than 0.12

[0520] ×: Less than 0.10 (including the same value and positive difference)

[0521] ((2) Strength (glass transition temperature: Tg))

[0522] Dynamic viscoelasticity was measured, and the temperature at which tanδ was maximized was determined and taken as the glass transition temperature (Tg). A high Tg indicates high strength over a wide temperature range. The measuring apparatus used was ARES (a trade name manufactured by TI Instruments). For the test samples, test pieces cut from the cured film (described later) with a length of 35 mm, a width of approximately 12.5 mm, and a thickness of 0.3 mm were used. Tg was measured under tensile conditions at a frequency of 10 rad / s and a measurement temperature ranging from -150 to 270 °C.

[0523] (3) Adhesion)

[0524] The resin compositions described below are coated onto a 35 μm thick copper foil and a polyimide film. After drying to remove the solvent, the mixture is heated and pressurized at 180°C for 1 hour to produce a laminate of the resin composition-copper foil or polyimide film for use in bonding samples.

[0525] A 1cm slit was cut into the laminated plate, and a copper foil or polyimide film was subjected to a peel test along a 90° direction at a tensile speed of 50mm / min. The peel strength was then measured. A higher peel strength value indicates higher adhesion.

[0526] (4) Preservation stability)

[0527] The condition of the varnish described below after standing at 30°C / 50% RH was observed and evaluated by the number of days until layer separation and / or precipitation of gel-like components, and the presence or absence of the following.

[0528] ◎: More than 120 days (including no precipitation)

[0529] ○: More than 90 days but less than 120 days

[0530] △: More than 30 days but less than 90 days

[0531] ×: Less than 30 days

[0532] [Examples 1-33], [Comparative Examples 1-20]

[0533] The resin composition was prepared according to the following preparation method using the mixing ratios shown in Tables 9-18: component (I): the modified hydrogenated block copolymers prepared above, and components (II) to (IV) below. It should be noted that in this embodiment, unless otherwise specified, "%" refers to mass.

[0534] <Component (II): Free radical initiator>

[0535] Perbutyl P-90 (manufactured by NOF Corporation)

[0536] <Component (III): Polar Resin>

[0537] Bisphenol A type epoxy resin EXA-850CRP (manufactured by DIC Corporation)

[0538] Phenoxy resin YP-50S (manufactured by Nippon Steel Chemical Co., Ltd.)

[0539] <Component (IV): Curing Agent>

[0540] 1-Benzyl-2-phenylimidazolium (Tokyo Chemical Industry Co., Ltd.)

[0541] Phenolic curing agent KA-1163 (manufactured by DIC Corporation)

[0542] (Preparation of cured film)

[0543] The cured film was prepared as follows. First, all components except the phenolic curing agent in the above composition were added to toluene, stirred, and dissolved to prepare a varnish with a concentration of 20% to 50% by mass. When using a phenolic curing agent, methyl ethyl ketone (using the premium grade manufactured by Wako Pure Chemical Industries, Ltd.) was used as a solvent to prepare a 50% by mass phenolic curing agent solution, which was then added to the above varnish and stirred to prepare a varnish (resin composition). The physical properties (adhesion) of each resin composition obtained were evaluated as above. The evaluation results are shown in Tables 9 to 18 below. The resin composition was coated onto a KAPTON film treated with an anti-stick coating at a speed of 30 mm / s, and then dried at 100°C for 30 minutes under a nitrogen flow using a blower dryer to obtain a film. The obtained film was cured at 200°C for 90 minutes under a nitrogen flow using a blower dryer to obtain a cured film. The cured film was used in the evaluation samples as described above, and the physical properties were evaluated. The evaluation results are shown in Tables 9 to 18. The above method was used to prepare bonding test pieces.

[0544] [Table 9]

[0545]

[0546] [Table 10]

[0547]

[0548] [Table 11]

[0549]

[0550] [Table 12]

[0551]

[0552] [Table 13]

[0553]

[0554] [Table 14]

[0555] [Table 15]

[0556]

[0557] [Table 16]

[0558]

[0559] [Table 17]

[0560]

[0561] [Table 18]

[0562]

[0563] As can be seen from Examples 1 to 33 and Comparative Examples 1 to 20, the modified block copolymer of this embodiment has an excellent balance of dielectric properties, strength and heat resistance as a cured product, and is particularly suitable for use in printed wiring boards using glass cloth, metal laminates and resin laminates.

[0564] [Examples 34-43], [Comparative Examples 21-33]

[0565] The following resin compositions were prepared according to the following preparation method using the following mixing ratios: (I) the modified hydrogenated block copolymers prepared above, and (II) to (IV) the following components, in the mixing ratios shown in Tables 18 to 21.

[0566] <Component (II): Free radical initiator>

[0567] Perbutyl C (manufactured by NOF Corporation)

[0568] Percumyl D (manufactured by Nippon Oil Co., Ltd.)

[0569] <Component (III): Polar Resin>

[0570] Polyphenylene oxide (PPE) resins are manufactured by polymerization as follows.

[0571] A 1.5-liter jacketed reactor with a nozzle for introducing oxygen-containing gas at the bottom, stirring turbine blades and baffles, and a reflux cooler on the exhaust line at the top of the reactor was used. The following solvents were added to the reactor: 0.2512 g of copper chloride dihydrate, 1.1062 g of 35% hydrochloric acid, 3.6179 g of di-n-butylamine, 9.5937 g of N,N,N',N'-tetramethylpropanediamine, 211.63 g of methanol, 493.80 g of n-butanol, and 180.0 g of 2,6-dimethylphenol containing 5 mol% 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane. The weight ratio of the solvents used was n-butanol:methanol = 70:30. Oxygen was then introduced into the reactor at a rate of 180 ml / min using the nozzle while vigorous stirring. Simultaneously, a heat transfer medium was circulated in the jacket to regulate the polymerization temperature, maintaining it at 40°C. The polymerization solution gradually became a slurry. When the polyphenylene ether reached the desired number average molecular weight, the aeration of the oxygen-containing gas was stopped, and the resulting polymerization mixture was heated to 50°C. Next, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added in small, incremental amounts, and the mixture was kept at 50°C until the slurry-like polyphenylene ether turned white. Then, 720 g of a methanol solution containing 36% hydrochloric acid at a ratio of 6.5% by mass was added, the mixture was filtered, and further washed repeatedly with methanol to obtain wet polyphenylene ether. Next, it was vacuum dried at 100°C to obtain dry polyphenylene ether. The ηsp / c was 0.103 dl / g, and the yield was 97%.

[0572] Regarding the determination of ηsp / c, the above-mentioned polyphenylene ether was prepared into a chloroform solution of 0.5 g / dl, and the specific viscosity (ηsp / c) at 30°C was determined using an Ubbelohde viscometer. It should be noted that the unit of specific viscosity (ηsp / c) is dl / g.

[0573] The obtained polyphenylene ether was modified as follows.

[0574] 152.5 g of the obtained polyphenylene ether and 152.5 g of toluene were mixed and heated to approximately 85°C. Next, 2.1 g of dimethylaminopyridine was added. When the solid had completely dissolved, 18.28 g of methacrylic anhydride was slowly added. The resulting solution was maintained at 85°C for 3 hours with continuous mixing. Next, the solution was cooled to room temperature to obtain a toluene solution of methacrylate-terminated polyphenylene ether. The obtained toluene solution was added dropwise in small increments to 1000 mL of methanol at 10°C in a 3 L cylindrical SUS container equipped with a homogenizer while stirring. The resulting powder was filtered, washed with methanol, and dried under nitrogen at 85°C for 18 hours.

[0575] <Component (IV): Crosslinking agent>

[0576] Triallyl isocyanurate (TAIC) TM(Manufactured by Mitsubishi Chemical Corporation)

[0577] (Preparation of cured film)

[0578] The cured film was prepared as follows. First, the above-mentioned components were added to toluene (using premium grade manufactured by Wako Pure Chemical Industries, Ltd.), stirred, and dissolved to prepare a varnish (resin composition) with a concentration of 20% to 50% by mass. The physical properties (adhesion) of the obtained resin compositions were evaluated as described above. The evaluation results are shown in Tables 19 to 22 below. The varnish was applied to a KAPTON film treated with an anti-sticking agent at a speed of 30 mm / s, and then dried at 100°C for 30 minutes under a nitrogen flow using a blower dryer to obtain a film. The obtained film was cured under a nitrogen flow using a blower dryer at 200°C for 90 minutes to obtain a cured film. The cured film was used as an evaluation sample as described above, and the physical properties were evaluated. The evaluation results are shown in Tables 19 to 22. Adhesion test pieces were prepared using the above method.

[0579] [Table 19]

[0580]

[0581] [Table 20]

[0582]

[0583] [Table 21]

[0584]

[0585] [Table 22]

[0586]

[0587] As can be seen from Examples 34-43 and Comparative Examples 21-33, the modified block copolymer of this embodiment has an excellent balance of dielectric properties, strength and heat resistance as a cured product, and is particularly suitable for use in printed circuit boards using glass cloth, metal laminates and resin laminates.

[0588] [Examples 44-51], [Comparative Examples 34-43]

[0589] The following resin compositions were prepared according to the following preparation method using the following mixing ratios: the modified hydrogenated block copolymers prepared above, and the following components (II) to (IV) as shown in Tables 22 to 25.

[0590] <Component (II): Free radical initiator>

[0591] Percumyl D (manufactured by Nippon Oil Co., Ltd.)

[0592] <Component (III): Polar Resin>

[0593] Polyimide resins

[0594] Bis(3-ethyl-5-methyl-4-maleimidephenyl)methane (BMI-70) (manufactured by KI Chemicals Co., Ltd.)

[0595] 4,4'-Bismaleimide diphenylmethane (BMI-H) (manufactured by KI Chemical Co., Ltd.)

[0596] <Component (IV): Curing Agent>

[0597] Cyanate ester-based curing agent: 2,2-bis(4-cyanate phenyl)propane (manufactured by Tokyo Chemical Co., Ltd.)

[0598] Diamine-based curing agent: 4,4'-Diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0599] (Preparation of cured film)

[0600] The cured film is prepared as follows. First, the polyimide resin is dissolved with a cyanate ester curing agent and / or a diamine curing agent in the mixing ratios described in Tables 22-25 at 160°C, and reacted for 6 hours with stirring to obtain a bismaleimide triazine resin oligomer.

[0601] The obtained bismaleimide triazine resin oligomer was dissolved in toluene, and the remaining components were added. The mixture was stirred and dissolved to prepare a varnish (resin composition) with a concentration of 20% to 50% by mass. The physical properties (adhesion) of each resin composition obtained as described above were evaluated. The evaluation results are shown in Tables 23 to 26 below. The varnish was applied to a KAPTON film treated with an anti-stick coating at a speed of 30 mm / s, and then dried in a nitrogen stream at 100°C for 30 minutes using a blower dryer to obtain a film. The obtained film was cured in a nitrogen stream at 200°C for a maximum of 90 minutes using a blower dryer to obtain a cured film. The cured film was used as an evaluation sample as described above, and the physical properties were evaluated. The evaluation results are shown in Tables 23 to 26.

[0602] [Table 23]

[0603]

[0604] [Table 24]

[0605]

[0606] [Table 25]

[0607]

[0608] [Table 26]

[0609]

[0610] As demonstrated in Examples 44-51 and Comparative Examples 34-43, the modified block copolymer of this embodiment exhibits an excellent balance of dielectric properties, strength, and heat resistance as a cured product. Therefore, it is particularly suitable for applications using this cured product in printed circuit boards employing glass cloth or metal laminates.

[0611] Industrial applicability

[0612] Regarding the modified block copolymer of the present invention, cured products, films, prepregs, especially resin compositions and / or varnishes and / or cured products containing the block copolymer, made using resin compositions and / or varnishes and / or cured products containing the block copolymer can be used as adhesives to obtain electronic circuit boards with excellent dielectric properties, heat resistance, strength, and adhesion to metal foils and resins as substrates, which have industrial applicability as next-generation communication substrates.

Claims

1. A modified block copolymer, comprising polymer blocks (A) mainly composed of vinyl aromatic compounds and polymer blocks (B) mainly composed of conjugated diene compounds, wherein, The copolymer contains more than 0.01% by mass of polar groups. The following conditions (i) to (iii) must be met: <Condition (i)> The total amount of polymer blocks (A) in the modified block copolymer, which are mainly composed of vinyl aromatic compounds, is 35% by mass or more. <Condition(ii)> The total content of Co, Ti, Ni and Li is below 90 ppm; <Condition (iii)> The weight-average molecular weight is 35,000 to 115,000.

2. The modified block copolymer of claim 1, wherein, The modified block copolymer was hydrogenated.

3. The modified block copolymer as described in claim 1 or 2, wherein, When the amount of 1,2-linked and / or 3,4-linked units (a) in the polymer block (B) is set to 100%, the amount of hydrogenated alkenyl monomer units (a1) in the unit (a) is 80% or more.

4. The modified block copolymer of claim 3, wherein, The polymer block (B) comprises the alkenyl monomer unit (a1) and a hydrogenated alkenyl monomer unit (b1) derived from the 1,4-linked unit (b). When the total content of the polymer block (B) is set to 100%, the total content of the alkenyl monomer unit (a1) and the alkenyl monomer unit (b1) is 90% or more.

5. The modified block copolymer as described in claim 1 or 2, wherein, The polar group is bonded to the polymer block (B).

6. The modified block copolymer as described in claim 1 or 2, wherein, The polar group is at least one selected from the group consisting of carboxyl, dicarboxyl, and anhydride groups.

7. The modified block copolymer as described in claim 1 or 2, wherein, The modified block copolymer contains 0.05% to 6.0% by mass of polar groups.

8. The modified block copolymer as described in claim 1 or 2, wherein, In condition (i), the total amount of polymer blocks (A) in the modified block copolymer, which are mainly composed of vinyl aromatic compounds, is 40% by mass or more.

9. The modified block copolymer as described in claim 1 or 2, wherein, In condition (iii), the weight-average molecular weight of the modified block copolymer is 40,000 to 110,000.

10. The modified block copolymer according to claim 1 or 2, wherein, When the total content of the polymer block (B) is set to 100%, the content of the unit (a) from 1,2-bonded and / or 3,4-bonded in the polymer block (B) is 15% to 85%.

11. A resin composition comprising: Component (I): The modified block copolymer according to any one of claims 1 to 10; and Select at least one from the group consisting of components (II) to (IV) below. Component (II): Free radical initiator; Component (III): Polar resin, excluding component (I); Component (IV): Curing agent, excluding component (II).

12. The resin composition of claim 11, wherein, The resin composition comprises component (III).

13. The resin composition of claim 11 or 12, wherein, The component (III) is at least one resin selected from the group consisting of epoxy resins, polyimide resins, polyphenylene ether resins, liquid crystal polyester resins, and fluorine resins.

14. The resin composition of claim 11 or 12, wherein, The component (III) is an epoxy resin.

15. A cured product comprising the modified block copolymer according to any one of claims 1 to 10.

16. An adhesive comprising the modified block copolymer according to any one of claims 1 to 10.

17. A cured product, which is a cured product of the resin composition according to any one of claims 11 to 14.

18. An adhesive comprising the resin composition according to any one of claims 11 to 14.

19. A resin film comprising the resin composition according to any one of claims 11 to 14.

20. A prepreg, which is a composite of a substrate and the resin composition according to any one of claims 11 to 14.

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

22. A laminate formed by laminating a cured resin composition of any one of claims 11 to 14 and / or a prepreg of claim 20 or 21 with a metal foil and / or a thermosetting resin.

23. The laminate as claimed in claim 22, wherein, The metal foil is copper foil, and the thermosetting resin is a polyimide resin.

24. A laminate formed by laminating a cured resin composition of any one of claims 11 to 14 and / or a cured prepreg of claim 20 or 21 with a metal foil.

25. An electronic circuit board material comprising the cured material as described in claim 15 or 17.

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